Cooperative Spin‐Crossover Behaviour in Polymeric 1D Fe II Coordination Compounds: [{Fe(tba) 3 }X 2 ]· n H 2 O

A new family of 1D cooperative spin-crossover polymers with general formula [{Fe(tba)3}X2]·nH2O [tba = N-(4H-1,2,4-triazol-4-yl)benzamide; X = CF3SO3–, n = 2 (1), n = 0 (4); BF4–,n = 3 (2), n = 0 (5); 4-CH3C6H4SO3–, n = 3 (3), n = 0 (6)] has been synthesised and characterised using a series of spectroscopic methods, X-ray powder diffraction, magnetic susceptibility measurements and differential scanning calorimetry. The copper analogue of 1, [{Cu(tba)3}(CF3SO3)2]·3H2O (7), has also been synthesised and its crystal structure solved at 293 K. Compound 7 crystallises in the P space group. The bidentate N-(4H-1,2,4-triazol-4-yl)benzamide ligand bridges the copper ions through the 1,2-nitrogen p…

Communication between iron(II) building blocks in cooperative spin transition phenomena

[EN] In the present article we discuss the cooperative nature of the spin crossover phenomenon in iron(II) complexes, providing a perspective of the state of the art in this area. The first aspect we discuss is the role of the intermolecular interactions, more precisely the ¿-interactions, in mononuclear complexes. We show that by playing with the nature of the ligands, aliphatic, aromatic, or extended aromatic, it is possible to create stronger cohesive forces and receive a more cooperative response from the compound. In the next step the singular family of bipyrimidine-bridged iron(II) dinuclear compounds is presented as the simplest example of polynuclear spin crossover complexes exhibit…

Enhanced bistability by guest inclusion in Fe(ii) spin crossover porous coordination polymers

Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN)(4)]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops of ca. 60 K wide centered near room temperature.

Influence of Host-Guest and Host-Host Interactions on the Spin-Crossover 3D Hofmann-type Clathrates {FeII(pina)[MI(CN)2]2·xMeOH (MI = Ag, Au)

[EN] The synthesis, structural characterization and magnetic properties of two new isostructural porous 3D compounds with the general formula {FeII(pina)[MI(CN)2]2}·xMeOH (x = 0¿5; pina = N-(pyridin-4-yl)isonicotinamide; MI = AgI and x ~ 5 (1·xMeOH); MI = AuI and x ~ 5 (2·xMeOH)) are presented. The single-crystal X-ray diffraction analyses have revealed that the structure of 1·xMeOH (or 2·xMeOH) presents two equivalent doubly interpenetrated 3D frameworks stabilized by both argentophilic (or aurophilic) interactions and interligand C¿O···HC H-bonds. Despite the interpenetration of the networks, these compounds display accessible void volume capable of hosting up to five molecules of methano…

A Novel Dinuclear Fe II Spin‐Crossover Complex Based on a 2,2‐Bipyrimidine Bridge Ligand: [Fe(CH 3 bipy)(NCS) 2 ] 2 bpym

The dinuclear iron(II) complex {[Fe(CH3bipy)(NCS)2]2bpym} has been synthesised and its crystal structure determined at 293 K. The magnetic properties display intramolecular antiferromagnetic coupling at 1 bar (J = −4.2 cm−1), and the onset of a pressure-induced spin conversion is observed at 11 kbar. Magnetic field Mossbauer measurements have been carried out at 4.2 K, and indicate that the HS species correspond to [HS-HS] pairs. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

ChemInform Abstract: Synthesis of Functionalized Indoles with a Trifluoromethyl-Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel-Crafts Alkylation with β-Trifluoromethyl-α,β-enones.

Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

Effect of Guest Molecules on Spin Transition Temperature in Loaded Hofmann‐Like Clathrates with Improved Porosity

The synthesis, crystal structure, magnetic and calorimetric studies of a new clathrate compound of the Hofmann-type spin crossover (SCO) metal-organic framework (MOF) {Fe(bpb)[MII(CN)4]}·xGuest (bpb = bis(4-pyridyl)butadiyne, and MII = Ni, Pt) with characteristic fsc topology is reported. The framework {Fe(bpb)[MII(CN)4]} can host up to 1.5 guest molecules of (trifluoromethyl)benzene and display complete one-step cooperative SCO behavior. Our systematic study on {Fe(bpb)[Pt(CN)4]}·xGuest shows a general reciprocal correlation between the SCO temperature with the volume of the guest molecules.

Synthesis of Densely Functionalised 5-Halogen-1,3-oxazin-2-ones byHalogen-Mediated Regioselective Cyclisation of N-Cbz-ProtectedPropargylic Amines: A Combined Experimental and Theoretical Study

A very efficient synthesis of 5-halogen-1,3-oxazin-2-ones has been accomplished by the halocyclisation reaction of chiral nonracemic N-carbobenzyloxy (N-Cbz)-protected propargylic amines by using I-2, Br-2 and Cl-2 as electrophile sources. The nature of the halogen influences the reaction time and yield. However, in all cases the reaction is totally regioselective taking place through a 6-endo-dig process regardless of the nature of the halogen and of the substituents in the starting material. To rationalise the experimental results, theoretical studies at the B3LYP/6-311G* level have been performed.

Organocatalytic enantioselective Strecker reaction with seven-membered cyclic imines

[EN] A highly enantioselective Strecker reaction with dibenzo[b,f][1,4]oxazepines has been described using a dihydroquinine-derived thiourea as organocatalyst. The reaction affords chiral 10,11-dihydrodibenzo[b,f][1,4] oxazepine 11-carbonitrile derivatives in excellent yields (up to 99%) and excellent enantioselectivities (up to 98%) under mild reaction conditions.

Catalytic Enantioselective Aza-Reformatsky Reaction with Cyclic Imines

A catalytic highly enantioselective aza-Reformatsky reaction with cyclic aldimines and ketimines for the synthesis of chiral b-amino esters with good yields and excellent enantioselectivities is reported.Areadily available diaryl prolinol is used as a chiral ligand, ZnMe2 as a zinc source and ethyl iodoacetate as reagent in the presence of air atmosphere. The reaction with cyclic ketimines generates a quaternary stereocenter with excellent levels of enantioselectivity. Furthermore, five-membered N-sulfonyl ketimines were used as electrophiles with good enantiomeric excesses, under the optimized reaction conditions. Moreover, several chemical transformations were performed with the chiral b-…

ChemInform Abstract: Highly Enantioselective Copper(I)-Catalyzed Conjugate Addition of 1,3-Diynes to α,β-Unsaturated Trifluoromethyl Ketones.

The conjugate diynylation of α,β-saturated trifluoromethyl ketones is carried out at low catalytic loading (2.5 mol% for aryl substituents) of a copper(I)—MeO-BIPHEP complex, triethylamine and a terminal 1,3-diyne.

Ferromagnetic Coupling through Spin Polarization in a Dinuclear Copper(II) Metallacyclophane.

[DT] Von organischen Radikalen zu Metallkomplexen konnte das bekannte Konzept für Ferroelektrika erfolgreich ausgedehnt werden: Die Abbildung zeigt ein Cyclophan-artiges Molekül mit einem Triplett-Grundzustand, in dem zwei CuII-Zentren von einem doppelten m-Phenylendiamid-Gerüst zusammengehalten werden.

Unprecedented multi-stable spin crossover molecular material with two thermal memory channels.

et al.

Regio‐, Diastereo‐, and Enantioselective Organocatalytic Addition of 4‐Substituted Pyrazolones to Isatin‐Derived Nitroalkenes

Hydroquinine 2,5‐diphenyl‐4,6‐pyrimidinediyl diether [(DHQ)2Pyr] catalyzed the regio‐, diastereo‐, and enantioselective addition of 4‐substituted pyrazolones to isatin‐derived nitroalkenes, providing a variety of chiral alkenylpyrazolone adducts containing a tetrasubstituted stereocenter bearing an oxindole moiety with excellent yields, regioselectivity, and diastereoselectivity, as well as a moderate enantioselectivity (up to 98 % yield, > 20:1 E/Z ratio dr and 78 % ee). The reaction harnesses a nitroalkene as an alkenylating agent through a Nucleophilic Vinylic Substitution (SNV) reaction.

Spin crossover in iron(II) complexes with ferrocene-bearing triazole-pyridine ligands.

In the search for new multifunctional spin crossover molecular materials, here we describe the synthesis, crystal structures and magnetic and photomagnetic properties of the complexes trans-[Fe(Fctzpy)2(NCX)2]·CHCl3 where Fc-tzpy is the ferrocene-appended ligand 4-(2-pyridyl)-1H-1,2,3-triazol- 1-ylferrocene, X = S (1) and X = Se (2). Both complexes display thermal- and light-induced (LIESST) spin crossover properties characterised by T1/2 = 85 and 168 K, ΔS = 55 and 66 J K−1 mol−1 , ΔH = 4.7 and 11.1 kJ mol−1 and TLIESST = 47 K and 39 K for 1 and 2 respectively. The crystal structure of 1 and 2 measured at 275 K is consistent with the iron(II) ion in the high-spin state while the crystal st…

NMR Spectroscopic Characterization and DFT Calculations of Zirconium(IV)-3,3′-Br2–BINOLate and Related Complexes Used in an Enantioselective Friedel–Crafts Alkylation of Indoles with α,β-Unsaturated Ketones

Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br-2-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti-IV and a dimeric structure in the cases of Zr-IV and Hf-IV. Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(R)-3,3'…

Guest induced reversible on–off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the population γHS(T) with high-spin (HS)-low-spin (LS) sequence: HS1LS0 (state 1) ↔ HS2/3LS1/3 (state 2) ↔ HS1/2LS1/2 (state 3) ↔ HS1/3LS2/3 (state 4) ↔ HS0LS1 (state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {FeII(3,8phen)[Au(CN)2]2}·xPhNO2 (3,8phen = 3,8-phenanthroline, PhNO2 = nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO2 guest (x = 1, 1·PhNO2) acts as a molecular wedge between the interp…

Thermal, pressure and light switchable spin-crossover materials

This article reviews the most relevant chemical and structural aspects that influence the spin-crossover phenomenon (SCO). Special attention is focussed on the recent development of SCO coordination polymers. The different approaches currently being explored in order to achieve multifunctionality in SCO materials are discussed.

Enantioselective zinc-mediated conjugate alkynylation of saccharin-derived 1-aza-butadienes

The enantioselective 1,4-alkynylation of conjugated imines derived from saccharin with aryl- and alkyl-substituted terminal alkynes has been achieved. The reaction mediated by diethylzinc in the presence of a catalytic amount of a bis(hydroxy)malonamide chiral ligand provides the corresponding imines bearing a propargylic stereocenter with moderate yields and fair to excellent enantioselectivities.

Symmetry breakings in a metal organic framework with a confined guest

The MOF $[{\text{Fe(tvp)}}_{2}{(\text{NCS})}_{2}]\ifmmode\cdot\else\textperiodcentered\fi{}2\text{BzCHO}$ is demonstrated to undergo a complex sequence of phase transitions and spin-crossover behavior of its constitutive ${\text{Fe}}^{\text{II}}$ ions upon adsorption of benzaldehyde guest molecules. Our study, combining Raman and synchrotron x-ray diffraction measurements on a single crystal, reveals that the conversion from the pure high-spin to the pure low-spin phases implies a rich sequence of intermediate phases, with symmetry breaking forming at least three different space groups. These different symmetries involve spin-state ordering, ligand ordering, and guest ordering, interpreted …

Organocatalytic Enantioselective Functionalization of Hydroxyquinolines through an Aza-Friedel-Crafts Alkylation with Isatin-derived Ketimines

[EN] A highly enantioselective addition of hydroxyquinolines to isatin-derived ketimines has been realized using a quinine-derived thiourea organocatalyst. The reaction affords chiral 3-amino-2-oxindoles bearing a quinoline moiety with a quaternary stereocenter in high yields (up to 98%) and excellent enantioselectivities (up to 99%). Moreover, we can extend this methodology for the enantioselective functionalization of 5-hydroxyisoquinoline. This methodology represents, to the best of our knowledge, the first enantioselective addition of hydroxyquinolines to imines.

Innenrücktitelbild: First Step Towards a Devil's Staircase in Spin-Crossover Materials (Angew. Chem. 30/2016)

Sequestering aromatic molecules with a spin-crossover Fe(II) microporous coordination polymer.

All in a spin: A series of three-dimensional porous coordination polymer {Fe(dpe)[Pt(CN)(4)]}⋅G (dpe = 1,2-di(4-pyridyl)ethylene; G = phenazine, anthracene, or naphthalene) exhibiting spin crossover and host-guest functions is reported. The magnetic properties of the framework are very sensitive to the chemical nature (aromatic or hydroxilic solvents) and the size of the included guest molecules.

Rational design of a new class of heterobimetallic molecule-based magnets: Synthesis, crystal structures, and magnetic properties of oxamato-bridged (M′=LiI and MnII; M=NiII and CoII) open-frameworks with a three-dimensional honeycomb architecture

Abstract Two new series of oxamato-bridged heterobimetallic coordination networks of general formula Li5[Li3M2(mpba)3(H2O)6] · 31H2O [M = NiII (1a) and CoII (1b)] and Li2[Mn3M2(mpba)3(H2O)6] · 22H2O [M = NiII (2a) and CoII (2b)] have been prepared from the metal-mediated self-assembly of the hexakis(bidentate), triple-stranded dinickel(II) and dicobalt(II) complexes [M2(mpba)3]8− [mpba = meta-phenylenebis(oxamato)] with either monovalent lithium(I) or divalent manganese(II) ions respectively, in water. X-ray structural analyses of 1a and 1b show an anionic three-dimensional network formed by an infinite parallel array of oxamato-bridged Li 3 I M 2 II (M = Ni and Co) hexagonal layers, which …

Sheets of alternating chirality in the structure of a novel iron(III) complex with a cyclic oxamide ligand

An organic–metalloorganic analogue of the inorganic clay minerals has been obtained from the cyclization of N,N′-bis(ethoxalyl)phenylenediamine in basic medium in the presence of iron(III) ions leading to formation of a cyclic oxamide ligand (L). The combination of intramolecular (covalent) interactions between metal and ligand and intermolecular (noncovalent) ionic interactions creates a novel layered compound with an intriguing crystal structure (shown on the right).

Synthesis, Crystal Structure and Magnetic Properties of [Fe(bpe)4(H2O)2](TCNQ)2 (bpe = trans-1,2-bis(4-pyridyl)ethane and TCNQ = tetracyanoquinodimethane)

The synthesis, structure and magnetic properties of [Fe(bpe)4(H2O)2](TCNQ)2 (1) are reported. 1 crystallizes in the triclinic P space group, a = 13.481(5), b = 14.887(3), c = 16.663(4) A, α = 101.048(18), β = 112.84(2), γ = 90.92(2)°, V = 3009.6(14) A3, Z = 2. The iron atom defines a compressed octahedron with the equatorial positions occupied by the bpe molecules which act as monodentate ligands and the two axial positions occupied by water molecules. The TCNQ− radical counterions are uncoordinated and interact by pairs defining (TCNQ)22− units strongly coupled antiferromagnetically. The iron(II) atoms are in the high spin state and its magnetic behaviour indicates the occurrence of zero-f…

Novel Iron(II) Microporous Spin-Crossover Coordination Polymers with Enhanced Pore Size

In this Communication, we report the synthesis and characterization of novel Hofmann-like spin-crossover porous coordination polymers of composition {Fe(L)[M(CN)4]}·G [L = 1,4-bis(4-pyridylethynyl)- benzene and MII = Ni, Pd, and Pt]. The spin-crossover properties of the framework are closely related to the number and nature of the guest molecules included in the pores.

Synthesis of Functionalized Indoles with a Trifluoromethy-Substituted Stereogenic Tertiary Carbon Atom Through an Enantioselective Friedel-Crafts Alkylation with beta-Trifluoromethyl-alpha, beta-enones

[EN] Chiral complexes of BINOL-based ligands with zirconium tert-butoxide catalyze the Friedel-Crafts alkylation reaction of indoles with beta-trifluoromethyl-alpha,beta-unsaturated ketones to give functionalized indoles with an asymmetric tertiary carbon center attached to a trifluoromethyl group. The reaction can be applied to a large number of substituted alpha-trifluoromethyl enones and substituted indoles. The expected products were obtained with good yields and ees of up to 99%.

Interaction between heterobinuclear molecules and nature of the ground spin state in oximato-bridged [CuIIMII]2 bis-binuclear complexes (M=Cu, Ni, Mn): crystal structure of [Cu(pdmg)Ni(Me3[12]N3)(EtOH)](ClO4)2

[EN] Two new heterobimetallic complexes [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](ClO4)(2)(2) and [Cu(pdmg) Mn(bipy)(2)]-ClO4)(2) . H2O (3) (H(2)pdmg = 3,9-dimethyl-4,8-diazaundeca-3,8-diene-2 10-dione dioxime; Me-3[12]N-3 = 2,4,4-trimethyl-1,5,9-triazacyclododeca-1-ene; bipy = 2,2'-bipyridyl) have been prepared and characterized. The structure of 2 has been determined by single-crystal X-ray diffraction methods. It consists of [Cu(pdmg)Ni(Me-3[12]N-3)(CH3CH2OH)](2+) cations and non-coordinated perchlorate anions. The [Cu(pdmg)(CH3CH2OH)] complex coordinates to the [Ni(Me-3[12]N-3)](2+) fragment to afford the binuclear unit doubly-bridged by oximato groups in cis arrangement. The coordination geo…

A thermal- and light-induced switchable one-dimensional rare loop-like spin crossover coordination polymer

Rare loop-like isostructural one-dimensional coordination polymer (1D-CP) systems formulated as {Fe(DPIP)2(NCSe)2}n·4DMF (1) and {Fe(DPIP)2(NCSe)2}n·4DMF (2) were obtained by self-assembling FeII and pseudohalide NCX−(X = S, Se) ions in presence of the V-shaped bidentate bridging ligand, namely, N,N′-dipyridin-4-ylisophthalamide (DPIP), and were characterized by elemental analysis, IR spectroscopy, TGA, single crystal X-ray diffraction and powder X-ray diffraction. The magnetic studies show that complex 2 undergoes a complete thermally induced spin crossover (SCO) behavior centered at T1/2 = 120 K with ca. 5 K thermal hysteresis loop and light-induced excited spin state trapping effect (LIE…

[Cr(dpa)(ox)2]–: a new bis-oxalato building block for the design of heteropolymetallic systems. Crystal structures and magnetic properties of PPh4[Cr(dpa)(ox)2], AsPh4[Cr(dpa)(ox)2], Hdpa[Cr(dpa)(ox)2]·4H2O, Rad[Cr(dpa)(ox)2]·H2O and Sr[Cr(dpa)(ox)2]2·8H2O (dpa = 2,2′-dipyridylamine)

[EN] The new complexes of formulae PPh4[Cr(dpa)(ox)(2)] (1), AsPh4[Cr(dpa)(OX)(2)] (2), Hdpa[Cr(dpa)(ox)(2)]-4H(2)O (3), Rad[Cr(dpa)(ox)(2)] . H2O (4) and Sr[Cr(dpa)(ox)(2)](2) . 8H(2)O (5) [PPh4 = tetraphenylphosphonium cation; AsPh4 = tetraphenylarsoniurn cation; dpa = 2,T-dipyridylamine; ox = oxalate dianion; Rad = 2-(4-N-methylpyridinium)4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-a-oxyl-3-N-oxide] have been prepared and characterised by single-crystal X-ray diffraction. The structures of 1-4 consist of discrete [Cr(dpa)(ox)(2)](-) anions, tetraphenylphosphonium. (1), tetraphenylarsonium (2), monoprotonated Hdpa (3) and univalent radical (4) cations and uncoordinated water molecules (2-…

Thermal-, pressure- and light-induced spin-crossover behviour in the two-dimensional Hofman-like coordination polymer [Fe(3-Clpy)2Pd(CN)4]

The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spincrossover behaviour at 298 K are discussed for the non-porous two-dimensional Hofmann-like coordination polymer [Fe(3-Clpy)(2)Pd(CN)(4)] (1). The title compound undergoes a two-step, cooperative thermal-induced SCO with critical temperatures T-c1(down arrow) = 159.6 K and T-c1(up arrow) = 164.5 K for the first step and T-c2(down arrow) = 141.4 K and T-c2(up arrow) = 148.4 K for the second step. Irradiation of the low-spin state with green light (514 nm) at 10 K induced the photoexcitation of around 60% of the iron(II) centres to the high-spin state (LIESST effect). The subseq…

Precise Control and Consecutive Modulation of Spin Transition Temperature Using Chemical Migration in Porous Coordination Polymers

Precise control of spin transition temperature (T(c)) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt(II)(CN)(4)]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T(c)(up) = 304 K and T(c)(down) = 284 K) and its iodine adduct {Fe(pz)[Pt(II/IV)(CN)(4)(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt(II), raised the T(c) by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe…

Chemistry and reactivity of dinuclear iron oxamate complexes: alkane oxidation with hydrogen peroxide catalysed by an oxo-bridged diiron(III) complex with amide and carboxylate ligation

[EN] A new dinuclear iron(III) complex with the tetradentate ligand N,N'-o-phenylenebis(oxamate) (opba) has been synthesised, and structurally, magnetically and electrochemically characterised. It possesses an unprecedented triply bridged Fe-2(mu-O)(mu-RCO2...H2O...O2CR)(2) core, whereby two N-amides from the opba ligand complete the square-pyramidal coordination sphere of the O-carboxylate rich iron site (Fe-N = 2.053 Angstrom and Fe-O = 2.015 Angstrom), The antiferromagnetic exchange interaction between the two high-spin Fe-III ions through the oxo bridge (J = -190 cm(-1); H = -JS(1)(.)S(2)) is weaker than that found in related mu-oxo singly bridged diiron(III) complexes. The lessened ant…

Guest Induced Strong Cooperative One- and Two-Step Spin Transitions in Highly Porous Iron(II) Hofmann-Type Metal-Organic Frameworks.

[EN] The synthesis, crystal structure, magnetic, calorimetric, and Mo¿ ssbauer studies of a series of new Hofmann-type spin crossover (SCO) metal¿organic frameworks (MOFs) is reported. The new SCO-MOFs arise from self-assembly of FeII, bis(4-pyridyl)butadiyne (bpb), and [Ag(CN)2] ¿ or [MII(CN)4] 2¿ (MII = Ni, Pd). Interpenetration of four identical 3D networks with ¿-Po topology are obtained for {Fe(bpb)[AgI (CN)2]2} due to the length of the rod-like bismonodentate bpb and [Ag(CN)2] ¿ ligands. The four networks are tightly packed and organized in two subsets orthogonally interpenetrated, while the networks in each subset display parallel interpenetration. This nonporous material undergoes a…

Chiral and Racemic Spin Crossover Polymorphs in a Family of Mononuclear Iron(II) Compounds

[EN] Understanding the origin of cooperativity and the equilibrium temperature of transition (T1/2) displayed by the spin-crossover (SCO) compounds as well as controlling these parameters are of paramount importance for future applications. For this task, the occurrence of polymorphism, presented by a number of SCO complexes, may provide deep insight into the influence of the supramolecular organization on the SCO behavior. In this context, herein we present a novel family of mononuclear octahedral FeII complexes with formula cis- [Fe(bqen)(NCX)2], where bqen is the chelating tetradentate ligand N,N¿-bis(8-quinolyl)ethane-1,2-diamine and X = S, Se. Depending on the preparation method, these…

A Combination of Visible-Light Organophotoredox Catalysis and Asymmetric Organocatalysis for the Enantioselective Mannich Reaction of Dihydroquinoxalinones with Ketones

[EN] An enantioselective photooxidative Mannich reaction of dihydroquinoxalinones with ketones by the merger of organophotoredox and asymmetric organocatalysis is described. This protocol features very mild reaction conditions using simple and cheap catalysts (Eosin Y and (S)-Proline) for the synthesis of chiral quinoxaline derivatives with good to high yields (up to 94%) and excellent enantioselectivities (up to 99% ee).

Enhanced Interplay between Host–Guest and Spin-Crossover Properties through the Introduction of an N Heteroatom in 2D Hofmann Clathrates

Controlled modulation of the spin-crossover (SCO) behavior through the sorption-desorption of invited molecules is an extensively exploited topic because of its potential applications in molecular sensing. For this purpose, understanding the mechanisms by which the spin-switching properties are altered by guest molecules is of paramount importance. Here, we show an experimental approach revealing a direct probe of how the interplay between SCO and host-guest chemistry is noticeably activated by chemically tuning the host structure. Thus, the axial ligand 4-phenylpyridine (4-PhPy) in the 2D Hofmann clathrates {Fe(4-PhPy)2[M(CN)4]} (PhPyM; M = Pt, Pd) is replaced by 2,4-bipyridine (2,4-Bipy),…

A wide family of pyridoxal thiosemicarbazone ferric complexes: Syntheses, structures and magnetic properties

Abstract This study reports the syntheses and the characterization of 12 ferric complexes of pyridoxal thiosemicarbazone. The richness of the coordination chemistry of this ligand is highlighted by the modulation of its charge from neutral H 2 L to anionic L 2− , thus leading to a wide family of ferric compounds with charge varying from +3 to −1. The structures of complexes [Fe(HL) 2 ]ClO 4  · 2H 2 O and [Fe(HL)L] · 4.5H 2 O were solved and discussed with a particular attention brought to the intermolecular interactions occurring between the complexes. The investigation of magnetic properties of these compounds revealed that two of them are in the HS state at any temperature, whereas the ot…

Inside Back Cover: First Step Towards a Devil's Staircase in Spin-Crossover Materials (Angew. Chem. Int. Ed. 30/2016)

International audience; Periodic and aperiodic spin-state concentration waves form during “Devil's staircase”-type spin-crossover in a new bimetallic 2D coordination polymer {Fe[(Hg(SCN)3)2](4,4′-bipy)2}n. In their Communication on page 8675 ff., J. A. Real, E. Collet et al. describe the appearance of spin-state concentration waves between long-range spatially ordered structures of low- and high-spin states during multistep spin-crossover.

A Singular Noninterpenetrating Coordination Polymer with the Pt3O4 Structure Containing Naked [Na+]4 Units

The homoleptic low-spin complex [Fe(L)3]2+ where L is the bisbidentate ligand 1,10-phenanthroline-5,6-dione, coordinates Na+ ions via exo-oriented dione groups defining a three-dimensional cationic network {[Fe(L)3]4Na3}11+}n with Pt3O4 topology. The large volume generated by the network is filled with 11 perchlorate ions, 7 "NaClO4" ionic pairs, and 9 H2O molecules. Singular [Na+]4 units, in which the Na+ ions are practically uncoordinated, are formed.

Electronic Structure Modulation in an Exceptionally Stable Non-Heme Nitrosyl Iron(II) Spin-Crossover Complex

The highly stable nitrosyl iron(II) mononuclear complex [Fe(bztpen)(NO)](PF6)(2) (bztpen=N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) displays an S=1/2 S=3/2 spin crossover (SCO) behavior (T-1/2=370 K, Delta H= 12.48 kJmol(-1), Delta S=33 JK(-1) mol(-1)) stemming from strong magnetic coupling between the NO radical (S=1/2) and thermally interconverted (S=0 S=2) ferrous spin states. The crystal structure of this robust complex has been investigated in the temperature range 120-420 K affording a detailed picture of how the electronic distribution of the t(2g)-e(g) orbitals modulates the structure of the {FeNO}(7) bond, providing valuable magneto-structural and spectroscopic correlat…

Fast detection of water and organic molecules by a change of color in an iron(II) microporous spin-crossover coordination polymer.

Here we present a novel three-dimensional iron(II) spin-crossover porous coordination polymer based on the bis(1,2,4-triazol-4-yl)adamantane (tr(2)ad) ligand and the [Au(CN)(2)](-) metalloligand anions with the formula {Fe(3)(tr(2)ad)(4)[Au(CN)(2))](2)}[Au(CN)(2)](4)·G. The sorption/desorption of guest molecules, water, and five/six-membered-ring organic molecules is easily detectable because the guest-free and -loaded frameworks present drastically distinct coloration and spin-state configurations.

Spin crossover behavior in a series of iron(III) alkoxide complexes.

The synthesis, crystal structures, magnetic behavior, and electron paramagnetic resonance studies of five new FeIII spin crossover (SCO) complexes are reported. The [FeIIIN5O] coordination core is constituted of the pentadentate ligand bztpen (N5) and a series of alkoxide anions (ethoxide, propoxide, n-butoxide, isobutoxide, and ethylene glycoxide). The methoxide derivative previously reported by us is also reinvestigated. The six complexes crystallize in the orthorhombic Pbca space group and show similar molecular structures and crystal packing. The coordination octahedron is strongly distorted in both the high- and low-temperature structures. The structural changes upon spin conversion ar…

Thermal and light induced polymorphism in iron(II) spin crossover compounds.

The spin crossover complexes {Fe[H2B(pz)2]2L} ([H2B(pz)2]2 = dihydrobis(pyrazolyl)borate, L = 2,2'-bipyridine (1), bipy and 1,10-phenanthroline, phen (2)) undergo both thermal and light induced spin crossover, but the structure of the low spin and light induced high spin states for 2 are different from that of the thermally induced high spin state and from those of 1. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

ChemInform Abstract: Organocatalytic Asymmetric Addition of Naphthols and Electron-Rich Phenols to Isatin-Derived Ketimines: Highly Enantioselective Construction of Tetrasubstituted Stereocenters.

A quinine-derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields (up to 99 %) with excellent enantioselectivity (up to 99 % ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines.

Enantioselective Synthesis of 5-Trifluoromethyl-2-oxazolines under Dual Silver/Organocatalysis.

[EN] The first enantioselective formal [3 + 2] cycloaddition between ¿-isocyanoesters and trifluoromethylketones to give 5-trifluoromethyl-2-oxazolines bearing two contiguous stereogenic centers, one of them being a quaternary stereocenter substituted with a CF3 group, has been developed. The reaction is based upon a multicatalytic approach that combines a bifunctional Brønsted base-squaramide organocatalyst and Ag+ as Lewis acid. The reaction could be achieved with a range of aryl and heteroaryl trifluoromethyl ketones, and the resulting oxazolines were obtained with good to excellent diastereo- and enantioselectivity.

Catalytic enantioselective addition of terminal alkynes to aromatic aldehydes using zinc-hydroxyamide complexes

[EN] A mandelamide ligand, derived from (S)-mandelic acid and (S)-phenylethanamine, catalyzes the addition of aryl-, alkyl-and silyl-alkynylzinc reagents to aromatic and heteroaromatic aldehydes with good yields and good to high enantioselectivities.

Enhanced porosity in a new 3D Hofmann-like network exhibiting humidity sensitive cooperative spin transitions at room temperature

The porous coordination polymers (PCPs) of general formula {Fe(bpac)[M(CN)4]}·guest (M = Pt, Pd) exhibit larger channels than previously synthesised 3D-Hofmann-like PCP. The channels are partially occupied by uncoordinated guest bpac ligands and labile H2O molecules. These PCPs exhibit very scarce cooperative spin crossover behaviour around room temperature with a large hysteresis loop (up to 49 K) and also display sensitivity to humidity and guest molecules. The inclusion of bpac molecules in the 3D network can be avoided by adding competitive volatile molecules during the crystallization process, affording the guest-free material. The spin crossover behavior of different guest and guest-f…

Crystal structure of the coordination polymer [FeIII2{PtII(CN)4}3]

[EN] The title complex, poly[dodeca--cyanido-diiron(III)triplatinum(II)], [FeIII2{PtII(CN)4}3], has a three-dimensional polymeric structure. It is built-up from square-planar [PtII(CN)4] 2 anions (point group symmetry 2/m) bridging cationic [FeIIIPtII(CN)4] + 1 layers extending in the bc plane. The FeII atoms of the layers are located on inversion centres and exhibit an octahedral coordination sphere defined by six N atoms of cyanide ligands, while the PtII atoms are located on twofold rotation axes and are surrounded by four C atoms of the cyanide ligands in a square-planar coordination. The geometrical preferences of the two cations for octahedral and square-planar coordination, respectiv…

Metal-Free Diastereo- and Enantioselective Dearomative Formal [3 + 2] Cycloaddition of 2-Nitrobenzofurans and Isocyanoacetate Esters

The diastereo- and enantioselective dearomative formal [3 + 2] cycloaddition of 2-nitrobenzofurans and α-aryl-α-isocyanoacetate esters provides tricyclic compounds bearing the 3a,8b-dihydro-1H-benzofuro[2,3-c]pyrrole framework with three consecutive stereogenic centers. The reaction was enabled by a cupreine-ether organocatalyst. The reaction products were obtained with almost full diastereoselectivity and with excellent enantiomeric excesses for a number of substituted 2-nitrobenzofurans and isocyanoacetates.

Enantioselective Synthesis of 4-Substituted Dihydrocoumarins through a Zinc Bis(hydroxyamide)-Catalyzed Conjugate Addition of Terminal Alkynes

A new enantioselective catalyst for the conjugate addition of terminal alkynes has been developed. Terminal alkynes react with 3-alkoxycarbonylcoumarins in the presence of diethylzinc and bis(hydroxyamide) ligands to give chiral non-racemic dihydrocoumarins substituted with an alkynyl group on the C-4 position with good yields and enantiomeric excesses up to 95%.

Reversible Chemisorption of Sulfur Dioxide in a Spin Crossover Porous Coordination Polymer

The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)4]} has been investigated at room temperature. Thermal analysis and adsorption-desorption isotherms showed that ca. 1 mol of SO2 per mol of {Fe(pz)[Pt(CN)4]} was retained in the pores. Nevertheless, the SO2 was loosely attached to the walls of the host network and completely released in 24 h at 298 K. Single crystals of {Fe(pz)[Pt(CN)4]}·nSO2 (n ≈ 0.25) were grown in water solutions saturated with SO2, and its crystal structure was analyzed at 120 K. The SO2 molecule is coordinated to the Pt(II) ion through the sulfur atom ion, Pt-S = 2.585(4) Å. This coordination…

Chemistry and reactivity of mononuclear manganese oxamate complexes: Oxidative carbon-carbon bond cleavage of vic-diols by dioxygen and aldehydes catalyzed by a trans-dipyridine manganese(III) complex with a tetradentate o-phenylenedioxamate ligand

[EN] Two new mononuclear octahedral manganese(III) complexes with the tetradentate equatorial ligand o-phenylenebis(oxamate) (opba) and two aquo (1a) or two pyridine (1b) axial ligands have been synthesized and characterized structurally, magnetically, and electrochemically. The cyclovoltammogram of 1a in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) shows an irreversible one-electron oxidation peak at a high anodic potential (E-ap = 1.03 V versus SCE), while that of 1b shows two well-separated one-electron oxidation peaks at moderate to high anodic potentials (E-ap = 0.92 and 1.27 V versus SCE), the first redox-wave being quasireversible in nature. The access to formally high-valent Mn-IV and…

Reversible guest-induced gate-opening with multiplex spin crossover responses in two-dimensional Hofmann clathrates.

Spin crossover (SCO) compounds are very attractive types of switchable materials due to their potential applications in memory devices, actuators or chemical sensors. Rational chemical tailoring of these switchable compounds is key for achieving new functionalities in synergy with the spin state change. However, the lack of precise structural information required to understand the chemical principles that control the SCO response with external stimuli may eventually hinder further development of spin switching-based applications. In this work, the functionalization with an amine group in the two-dimensional (2D) SCO compound {Fe(5-NH2Pym)2[MII(CN)4]} (1M, 5-NH2Pym = 5-aminopyrimidine, MII =…

[Fe(TPT)(2/3){M(I)(CN)2}2]⋅nSolv (M(I) = Ag, Au): new bimetallic porous coordination polymers with spin-crossover properties.

Two new heterobimetallic porous coordination polymers with the formula [Fe(TPT)2/3{MI(CN)2}2]¿nSolv (TPT=[(2,4,6-tris(4-pyridyl)-1,3,5-triazine]; MI=Ag (nSolv=0, 1¿MeOH, 2¿CH2Cl2), Au (nSolv=0, 2¿CH2Cl2)) have been synthesized and their crystal structures were determined at 120¿K and 293¿K by single-crystal X-ray analysis. These structures crystallized in the trigonal R-3m space group. The FeII ion resides at an inversion centre that defines a [FeN6] coordination core. Four dicyanometallate groups coordinate at the equatorial positions, whilst the axial positions are occupied by the TPT ligand. Each TPT ligand is centred in a ternary axis and bridges three crystallographically equivalent Fe…

Dinuclear Iron(II) Spin Crossover Compounds: Singular Molecular Materials for Electronics

Dinuclear spin crossover molecules can adopt three different spin-pair states: a fully diamagnetic low spin state, [LS–LS], with both iron(II) atoms in the LS state; a paramagnetic mixed spin-pair state [LS–HS]; and an antiferromagnetically coupled [HS–HS] state. Stabilisation of the [LS–HS] state depends on a subtle balance between intra- and inter-molecular interactions in the solid state, consequently, the thermal dependence of the physical and structural properties can present one-step or two-step spin transitions. The former case involves the [LS–LS] ↔ [HS–HS] transformation while in the latter case the intermediate stage responsible for the plateau, at 50% conversion between the two s…

Diastereoselective Michael addition of (S)-mandelic acid enolate to 2-arylidene-1,3-diketones: enantioselective diversity-oriented synthesis of densely substituted pyrazoles

[EN] A diversity-oriented approach to enantiomerically pure densely substituted pyrazoles, ¿-aryl-¿-pyrazolylatrolactic acid and ¿-aryl-¿-pyrazolylacetophenones has been developed. The approach utilises the conjugated addition of the lithium enolate of the (2S,5S)-cis-1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde to several 2-arylidene-1,3-diketones, which proceeds readily to give the corresponding Michael adducts in good yields and diastereoselectivities. The cyclocondensation of the 1,3-diketone moieties present in Michael adducts with several hydrazines leads to enantiomerically pure densely substituted pyrazoles. Subsequent basic hydrolysis of the …

Enantioselective synthesis of chiral oxazolines from unactivated ketones and isocyanoacetate esters by synergistic silver/organocatalysis

[EN] A multicatalytic approach that combines a bifunctional Brønsted base¿squaramide organocatalyst and Ag+ as Lewis acid has been applied in the reaction of unactivated ketones with tert-butyl isocyanoacetate to give chiral oxazolines bearing a quaternary stereocenter. The formal [3+2] cycloaddition provided high yields of the corresponding cis-oxazolines with good diastereoselectivity and excellent enantioselectivity, being applied to aryl¿alkyl and alkyl¿alkyl ketones.

ChemInform Abstract: Enantioselective Synthesis of 4-Substituted Dihydrocoumarins Through a Zinc Bis(hydroxyamide)-Catalyzed Conjugate Addition of Terminal Alkynes.

Terminal alkynes (II) react with coumarins (I) in the presence of diethylzinc and chiral bis(hydroxyamide) ligands to give enantiopure dihydrocoumarins (III) substituted with an alkynyl group in C(4) position in good enantioselectivities.

An unprecedented hetero-bimetallic three-dimensional spin crossover coordination polymer based on the tetrahedral [Hg(SeCN)4]2− building block

[EN] Self-assembly of octahedral FeII ions, trans-1,2-bis(4-pyridyl) ethane (bpe) bridging ligands and [Hg(XCN)(4)](2-) (X = S (1), Se (2)) tetrahedral building blocks has afforded a new type of hetero-bimetallic Hg-II-Fe-II spin-crossover (SCO) 3D 6,4-connected coordination polymer (CP) formulated {Fe(bpe)[Hg(XCN)(4)]}(n). For X = S (1), the ligand field is close to the crossing point but 1 remains paramagnetic over all temperatures. In contrast, for X = Se (2) the complex undergoes complete thermal induced SCO behaviour centred at T-1/2 = 107.8 K and complete photoconversion of the low spin state into a metastable high-spin state (LIESST effect) with T-LIESST = 66.7 K. The current results…

Imparting hysteretic behavior to spin transition in neutral mononuclear complexes

A series of spin transition neutral compounds [FeL(NCS)2] has been synthesized and characterized by means of magnetic susceptibility studies, X-ray diffraction, IR and Mossbauer spectroscopic, and calorimetric measurements (L = N,N-bis((3-alkoxypyridin-2-yl)methylene)-propane-1,3-diamine, number of carbon atoms in chains (n) = 4, 12, 14, 16, 18, 20). The shortest chain compound is crystalline and displays a gradual spin transition above ambient temperature. Growing the aliphatic substituent up to n = 12 and 14 leads to loss of crystalline order and deterioration of magnetic properties. At the critical chain length n = 16 and above, the compounds undergo a phase transition reflected by a spi…

Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Surfaces

Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {FeII(Lax)2[MII(CN)4]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the MII derivatives (MII = Pd and Pt) with sulfur-rich axial ligands (Lax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for PtII-methyl and PtII/PdII-ethyl derivatives, while the PdII-methyl deri…

Supramolecular isomerism in spin crossover networks with aurophilic interactions

Assembly of FeII, 3-cyanopyridine and [Au(CN)2]– affords, in one-pot reaction, three coordination polymers that represent a genuine example of supramolecular isomerism with strong influence in the spin crossover regime of the FeII ions. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

Manganese(iv) oxamato-catalyzed oxidation of secondary alcohols to ketones by dioxygen and pivalaldehyde

A new manganese(IV) oxamato complex possessing a bis(moxo) dimanganese core has been synthesized, magnetically and structurally characterized, and found to catalyze the aerobic oxidation of secondary alcohols to ketones with cooxidation of pivalaldehyde to pivalic acid with good yields and high selectivities. Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Fernandez Picot, Isabel, Isabel.Fernandez@uv.es ; Pedro Llinares, Jose Ramon, Jose.R.Pedro@uv.es ; Rosello Arce, Antonio Luis, Antonio.L.Rosello@uv.es ; Castro Bleda, Isabel, Isabel.Castro@uv.es

Enantioselective Friedel-Crafts Alkylation of Indoles with (E)-1-Aryl-4-benzyloxybut-2-en-1-ones Catalyzed by an (R)-3,3′-Br2BINOLate-Hafnium(IV) Complex

A highly enantioselective Friedel–Crafts reaction of unprotected indoles with (E)-1-aryl-4-benzyloxybut-2-en-1-ones catalyzed by a new chiral [Hf{(R)-3,3′-Br2-BINOL}(OtBu)2]2 complex has been developed to functionalize the C-3 position of the indole nucleus with a side chain bearing a 1,4-difunctionalized moiety and a benzylic stereogenic center. The reaction proceeds in good to excellent yields and excellent enantioselectivities (up to 97 % ee). The usefulness of this approach was illustrated with the synthesis of a tryptophol derivative.

Synyhesis, structure, spectroscopy and redox chemistry of square-planar nickel(II) complexes with tetradentate o-phenylenedioxamidates and related ligands

[EN] A series of four-coordinate square-planar nickel(II) complexes of o-phenylenebis(N¿-methyloxamidate) (L1) and related o-phenylene(N¿-methyloxamidate)oxamate (L2) and o-phenylenebis(oxamate) (L3) tetradentate ligands have been synthesized and characterized structurally, spectroscopically and electrochemically. The parent nickel(II)¿L1 complex presents an intense MLCT band in the UV region (¿max = 357 nm) and a distinctive 1 s ¿ 4p CT satellite in the Ni K-edge XANES spectrum (E = 8339.2 eV). These features together with the short Ni¿N(amidate) bond lengths (1.85¿1.93 Å) as revealed by the analysis of the Ni K-edge EXAFS spectrum and confirmed by single-crystal X-ray diffraction are typi…

Discrimination between two memory channels by molecular alloying in a doubly bistable spin crossover material

[EN] A multistable spin crossover (SCO) molecular alloy system [Fe1-xMx(nBu-im)(3)(tren)](P1-yAsyF6)(2) (M = Zn-II, Ni-II; (nBu-im)(3)(tren) = tris(n-butyl-imidazol(2-ethylamino))amine) has been synthesized and characterized. By controlling the composition of this isomorphous series, two cooperative thermally induced SCO events featuring distinct critical temperatures (T-c) and hysteresis widths (Delta T-c, memory) can be selected at will. The pristine derivative 100As (x = 0, y = 1) displays a strong cooperative two-step SCO and two reversible structural phase transitions (PTs). The low temperature PTLT and the SCO occur synchronously involving conformational changes of the ligand's n-buty…

ChemInform Abstract: Enantioselective LaIII-pyBOX-Catalyzed Nitro-Michael Addition to (E)-2-Azachalcones.

A [La(OTf)3] complex with a new pyBOX ligand bearing a bulky 1-naphthylmethyl substituent at the 4′-position of the oxazoline ring catalyzes the conjugate addition of nitroalkanes to a broad range of (E)-2-azachalcones, providing the expected nitro-Michael products with good yields and enantiomeric excesses up to 87 %. The optical purity of the products can be increased by a single crystallization. A plausible stereochemical model to account for the observed stereochemistry has been proposed.

Catalytic Diastereo- and enantioselective vinylogous Mannich reaction of alkylidenepyrazolones to isatin-derived ketimines

A valuable organocatalytic vinylogous Mannich reaction between alkylidenepyrazolones and isatin-derived ketimines has been successfully established. Squaramide organocatalyst, prepared from quinine, catalyzed the diastereo- and enantioselective vinylogous Mannich addition, affording a range of aminooxindole-pyrazolone adducts (24 examples) with excellent outcomes: up to 98% yield with complete diastereoselectivity and excellent enantioselectivity (up to 99% ee). Additionally, different synthetic transformations were performed with the chiral pyrazolone-oxindole adducts.

Thermal, Pressure and Light Induced Spin Transition in the Two-Dimensional Coordination Polymer [Fe(pmd)2[Cu(CN)2]2]

[EN] A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer {Fe(pmd)(2)[Cu(CN)(2)](2)} is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light ( lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 angstrom(3) which is lower than the usually observed value of around 25-30 angstrom(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 angstrom. The structural data of the irradiated state indicate that the high spin state is well induced since the …

A study of the exchange interaction through phenolato, oximato and oxamidato bridges in MnIICuII dimers. Crystal structure of [Cu(salen)Mn(hfa)2]

Abstract Three new heterodinuclear CuIIMnII complexes of formula [Cu(salen)Mn(hfa)2] (1), [Cu(pdmg)Mn(phen)2](ClO4)2·2.5H2O (2) and [Cu(apox)Mn(bpy)2](ClO4]2·0.5H2O (3) (salen=N,N′-ethylenebis(salicylideneiminate), hfa=hexafluoroacetylacetonate, pdmg=3,9-dimethyl-4,8-diazaundeca-3,8-diene-2,10-dione dioximate, phen=1,10- phenanthroline, apox=N,N′-bis(3-aminopropyl)oxamidate and bipy=2,2′-bipyridyl) have been synthesized. The crystal and molecular structure of 1 has been determined by X-ray diffraction methods. It crystallizes in the triclinic system, space group P 1 with cell constants a=15.584(4), b=12.039(3), c=9.470(2) A, α=113.83(2), β=107.17(3), γ=84.28(3)°; V=1552(1) A3, D (calc., Z=2…

Regio- and Stereoselective Synthesis of 3-Pyrazolylidene-2-oxindole Compounds by Nucleophilic Vinylic Substitution of (E)-3-(Nitromethylene)indolin-2-one

[EN] A highly regio- and stereoselective synthesis of 3-alkylidene-2-oxindoles has been described through a nucleophilic vinylic substitution (SNV) of (E)-3-(nitromethylene)indolin-2-one using pyrazol-3-ones as nucleophiles and Et3N as a base. The reaction affords selectively the Z-isomer when pyrazol-3-ones without substituents at the 4 position are used. While the reaction is E-selective with 4- substituted pyrazolones. The stereoselectivity (up to >20:1) and the yields (up to 98%) are very high under mild reaction conditions.

Cooperative Thermal and Optical Switching of Spin States in a New Two-Dimensional Coordination Polymer

{Fe(pmd)2[Cu(CN)2]2} (pmd = pyrimidine) displays a rigid two-dimensional structure and undergoes thermal- and optical-driven spin crossover behaviour; cooperative elastic coupling between iron(II) ions in the framework induces thermal hysteresis in the HS↔LS conversion and sigmoidal HS→LS relaxation of the photo-induced HS state at low temperatures. Niel, Virginie, Virginie.Niel@uv.es ; Galet Domingo, Ana Guadalupe, Ana.Galet@uv.es ; Gaspar Pedros, Ana Belen, Ana.B.Gaspar@uv.es ; Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

Pertosylated polyaza[n](9,10)anthracenophanes

Abstract Pertosylated polyaza[n](9,10)antracenophanes have been obtained in high yields by a modification of the Richman-Atkins methodology. Molecular Mechanics calculations as well as the crystal structure of the N,N′,N″,N‴-Tetratosyl-2,6,9,13-tetraaza[14](9,10)anthracenophane 4 derivative reveal the existence of a well defined cavity where both the aromatic moiety and the nitrogen donor atoms converge. Reduced mobility of the aliphatic chain is also observed as well as the presence of some strain at the benzylic positions.

Extrinsicvs.intrinsic luminescence and their interplay with spin crossover in 3D Hofmann-type coordination polymers

The research of new multifunctional materials, as those undergoing spin crossover (SCO) and luminescent properties, is extremely important in the development of further optical and electronic switching devices. As a new step towards this ambitious aim, the coupling of SCO and fluorescence is presented here following two main strategies: whether the fluorescent agent is integrated as a part of the main structure of a 3D SCO coordination polymer {FeII(bpan)[MI(CN)2]2} (bpan = bis(4-pyridyl)anthracene, MI = Ag (FebpanAg), Au (FebpanAu)) or is a guest molecule inserted within the cavities of the 3D switchable framework {FeII(bpb)[MI(CN)2]2}·pyrene (bpb = bis(4-pyridyl)butadiyne, MI = Ag (FebpbA…

A Cu-BOX catalysed enantioselective Mukaiyama-aldol reaction with difluorinated silyl enol ethers and acylpyridine

A Cu(II)/BOX complex catalyses the enantioselective addition of difluorinated silyl enol ethers to acylpyridine N-oxides. The reaction provides difluorinated chiral tertiary alcohols of great interest in medicinal chemistry. These compounds are obtained in moderate to excellent yields and with high enantioselectivities. The stereochemical outcome of the reaction has been explained by DFT calculations.

ChemInform Abstract: Catalytic Enantioselective Addition of Terminal Alkynes to Aromatic Aldehydes Using Zinc-Hydroxyamide Complexes.

A mandelamide ligand, derived from (S)-mandelic acid and (S)-phenylethanamine, catalyzes the addition of aryl-, alkyl- and silyl-alkynylzinc reagents to aromatic and heteroaromatic aldehydes with good yields and good to high enantioselectivities.

Highly Enantio- and Diastereoselective Inverse Electron Demand Hetero-Diels-Alder Reaction using 2-Alkenoylpyridine N-Oxides as Oxo-Heterodienes

A general catalytic inverse electron demand hetero-Diels Alder reaction for 2-alkenoylpyridine N-oxides is presented. 2-Alkenoylpyridine N-oxides react very efficiently with alkenes in the presence of bisoxazolidine-copper(II) [BOX-Cu(II)] complexes to give chiral dihydropyrans bearing a pyridine ring at the 6-position with very high yields and excellent diastereo- and enantioselectivity. These heterodienes exhibited higher reactivity and enantioselectivity than the corresponding non-oxidized 2-alkenoylpyridines.

ChemInform Abstract: Aza-Henry Reaction of Isatin Ketimines with Methyl 4-Nitrobutyrate en Route to Spiro[piperidine-3,3′-oxindoles].

A new enantioselective route to spiro[piperidine-3,3′-oxindoles] from isatin ketimines is described. The aza-Henry reaction of N-Boc-isatin ketimines with methyl 4-nitrobutyrate in the presence of a Ph2BOX-CuBr2 complex provided the corresponding nitro amino esters with good diastereoselectivity and excellent enantioselectivity (up to >99% ee). The aza-Henry adducts were transformed into spiro[piperidine-3,3′-oxindoles] after reduction of the nitro group to oxime, and cleavage of the N-Boc group and lactamisation.

Enantioselective alkynylation of benzo[e][1,2,3]-oxathiazine 2,2-dioxides catalysed by (R)-VAPOL-Zn complexes: synthesis of chiral propargylic cyclic sulfamidates

[EN] (R)-VAPOL-Zn(II) complexes catalysed the enantioselective addition of terminal alkynes to cyclic benzoxathiazine 2,2-dioxides, providing the corresponding chiral propargylic sulfamidates with high yields (up to 93%) and good enantiomeric excesses (up to 87%).

Clathration of Five-Membered Aromatic Rings in the Bimetallic Spin Crossover Metal–Organic Framework [Fe(TPT)2/3{MI(CN)2}2]·G (MI = Ag, Au)

Six clathrate compounds of the three-dimensional spin crossover metal−organic framework formulated [Fe(TPT)2/3{MI (CN)2}2]· nG, where TPT is 2,4,6-tris(4-pyridyl)-1,3,5-triazine, MI = Ag or Au and G represent the guest molecules furan, pyrrole and thiophene, were synthesized using slow diffusion techniques. The clathrate compounds were characterized by single-crystal X-ray diffraction at 120 and 300 K, thermogravimetric analysis and thermal dependence of the magnetic susceptibility. All compounds crystallize in the R3̅ m trigonal space group. The FeII defines a unique [FeN6] crystallographic site with the equatorial positions occupied by four dicyanometallate ligands while the axial positio…

Iron(iii) oxamato-catalyzed epoxidation of alkenes by dioxygen and pivalaldehyde

A new iron(III)–carbonato monomeric complex of orthophenylenebis( oxamato) (opba) 1 is synthesized, and spectroscopically and structurally characterized; it is a moderately efficient non-heme catalyst for the aerobic epoxidation of alkenes with co-oxidation of pivalaldehyde. Ruiz Garcia, Rafael, Rafael.Ruiz@uv.es ; Fernandez Picot, Isabel, Isabel.Fernandez@uv.es ; Pedro Llinares, Jose Ramon, Jose.R.Pedro@uv.es

Strong Cooperative Spin Crossover in 2D and 3D FeII −MI,II HofmannLike Coordination Polymers Based on 2‑Fluoropyrazine

Self-assembling iron(II), 2-fluoropyrazine (Fpz), and [MII(CN)4] 2− (MII = Ni, Pd, Pt) or [AuI (CN)2] − building blocks have afforded a new series of two- (2D) and threedimensional (3D) Hofmann-like spin crossover (SCO) coordination polymers with strong cooperative magnetic, calorimetric, and optical properties. The iron(II) ions, lying on inversion centers, define elongated octahedrons equatorially surrounded by four equivalent centrosymmetric μ4-[MII(CN)4]2− groups. The axial positions are occupied by two terminal Fpz ligands affording significantly corrugated 2D layers {Fe(Fpz)2([MII(CN)4]}. The Pt and Pd derivatives undergo thermal- and light-induced SCO characterized by T1/2 temperatur…

Coordination polymers undergoing spin crossover and reversible ligand exchange in the solid

Here we report the synthesis and characterisation of a polymer made up of a system of parallel 2-D grids of Fe(II) ions linked by [Au(CN)2]– bridges and its transformation into a new system of three interpenetrated 3-D coordination open frameworks with the NbO topology. Reversibility of this crystal-to-crystal transformation is evidenced by X-ray crystallographic data and from their spin crossover properties. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es

Enantioselective synthesis of 2-substituted-1,4-diketones from (S)-mandelic acid enolate and α,β-enones

[EN] An approach for the synthesis of chiral non-racemic 2-substituted-1,4-diketones from (S)-mandelic acid and ¿,ß-enones has been developed. The reaction of lithium enolate of the 1,3-dioxolan-4-one derived from optically active (S)-mandelic acid and pivalaldehyde with ¿,ß-unsaturated carbonyl compounds proceeds readily to give the corresponding Michael adducts in good yields and with high diastereoselectivities. The addition of HMPA (3 equiv) reverses and strongly enhances the diastereoselectivity of the reaction. A change in the reaction mechanism from a lithium catalyzed to the one where catalysis has been suppressed by coordination of HMPA to lithium is proposed to explain these resul…

Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin-Crossover Coordination Polymer

Catalytic Diastereo- and Enantioselective Synthesis of Tertiary Trifluoromethyl Carbinols through a Vinylogous Aldol Reaction of Alkylidenepyrazolones with Trifluoromethyl Ketones

A diastereo- and enantioselective organocatalytic aldol reaction between alkylidenepyrazolones and trifluoromethyl ketones leading to chiral tertiary alcohols bearing a trifluoromethyl group is presented. The methodology is based on the use of a bifunctional organocatalyst in order to activate the γ-hydrogen atoms of the alkylidenepyrazolone nucleophile and the carbonyl group of the trifluoromethylarylketone providing highly functionalized trifluoromethyl alcohols with moderate yields, excellent diastereoselectivity, and moderate to good enantioselectivity. Experiments monitoring the conversion by 1H NMR and the enantiomeric excess by HPLC with the reaction time showed that full conversion …

Pressure Effect Investigations on the Spin Crossover Systems{Fe[H 2 B(pz) 2 ] 2 (bipy)} and {Fe[H 2 B(pz) 2 ] 2 (phen)}

Pressure effect studies on the spin crossover behaviour of the mononuclear compounds {Fe[H2B(pz)2]2(bipy)}(1) and {Fe[H2B(pz)2]2(phen)}(2) have been performed in the range of 105 Pa–1.02 GPa at variable temperatures (100–310 K). Continuous spin transitions and displacement of its characteristic temperature has been observed for 1 with increasing pressure. Meanwhile the response of 2 under applied pressures is quite unexpected, and can only be understood in terms of a crystallographic phase transition or change in the bulk modulus of the compound. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Ein neuartiger Eisen(III)-Komplex mit einem cyclischen Amidliganden und einer Struktur aus Schichten alternierender Chiralität

Ein organisch-metallorganisches Analogon von Tonmineralien wurde unter Cyclisierung von N,N′-Bis(ethoxalyl)phenylendiamin zu einem zweizahnigen Oxamid-Liganden (L) in basischem Medium und in Gegenwart von Eisen(III)-Ionen erhalten. Das Zusammenwirken von intramolekularen (kovalenten) Wechselwirkungen zwischen Metall und Ligand und intermolekularen (nichtkovalenten) ionischen Wechselwirkungen fuhrt dabei zu einer neuartigen Schichtverbindung mit einer faszinierenden Kristallstruktur (siehe rechts).

ChemInform Abstract: Organocatalytic Enantioselective Friedel-Crafts Alkylation of 1-Naphthol Derivatives and Activated Phenols with Ethyl Trifluoropyruvate.

Financial support from the MINECO [Gobierno de Espana and FEDER (EU)] (CTQ2013-47949-P) and from Generalitat Valenciana (ISIC2012/001) is gratefully acknowledged. M.M.-M. thanks the Universitat de Valencia for a predoctoral grant. C. V. thanks MINECO for JdC contract. Access to NMR and MS facilities from the Servei central de support a la investigacio experimental (SCSIE)-UV is also acknowledged.

Organocatalytic asymmetric addition of naphthols and electron-rich phenols to isatin-derived ketimines: highly enantioselective construction of tetrasubstituted stereocenters.

A quinine-derived thiourea organocatalyst promoted the highly enantioselective addition of naphthols and activated phenols to ketimines derived from isatins. The reaction afforded chiral 3-amino-2-oxindoles with a quaternary stereocenter in high yields (up to 99%) with excellent enantioselectivity (up to 99% ee). To the best of our knowledge, this transformation is the first highly enantioselective addition of naphthols to ketimines

Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation with (E)-1,4-Diaryl-2-butene-1,4-diones

Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…

Structural, magnetic and calorimetric studies of a crystalline phase of the spin crossover compound [Fe(tzpy)2(NCSe)2]

The compound [Fe(tzpy)2(NCSe)2] (tzpy = 3-(2-pyridyl)-[1,2,3]triazolo[1,5-a]pyridine)) has been synthesized and its crystal structure, magnetic behavior and calorimetric properties investigated. Samples constituted of single crystals of [Fe(tzpy)2(NCSe) 2] display a relatively cooperative spin-state change centered at T1/2 ¿ 251.7 K with a hysteresis loop 3.5 K wide. The average enthalpy (¿H) and entropy (¿S) changes upon the spin crossover behavior (SCO) obtained from DSC measurements are 11.1 ± 0.4 kJ mol -1 and 44.5 ± 3 J K-1 mol-1, respectively. The magnetic and calorimetric data have been satisfactorily simulated using the mean-field regular solution model (Slichter-Drickamer) and the …

Organocatalytic Enantioselective Synthesis of Pyrazoles Bearing a Quaternary Stereocenter

An efficient one-pot asymmetric synthesis of pyrazoles bearing a chiral quaternary stereocenter has been developed. Quinine-derived thiourea catalyzed the enantioselective addition of pyrazolones to isatin-derived ketimines, providing the corresponding acetylated pyrazoles after in situ treatment with Ac2O/Et3N. The corresponding pyrazoles were afforded in high yields and excellent enantioselectivities.

An Na8 Cluster in the Structure of a Novel oxamato-bridged Na'Cu'' three-Dimensional Coordination Polymer

[EN] The new heterometallic sodium(I)¿copper(II) compound Na4Cu2 (2) · 10.5 H2O (3), where H8[2] stands for N,N',N'',N'''-methanetetrayltetrakismethylenetetrakis(oxamic acid), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. The structure of 3 consists of cationic [Cu2(¿4:¿4-2)]4- dinuclear units, coordinated sodium cations, and water molecules. In the crystal, the dinuclear copper entities are joined through discrete aggregates of eight sodium atoms linked by oxamato and water bridges, leading to a three-dimensional polymeric network.

Innentitelbild: Bidirectional Chemo‐Switching of Spin State in a Microporous Framework (Angew. Chem. 26/2009)

Das chemische Schalten des Magnetismus in zwei Richtungen wurde in einem mikroporosen Koordinationspolymer mit Spin-Crossover-Einheiten beobachtet. M. Ohba, J. A. Real, S. Kitagawa und Mitarbeiter stellten in ihrer Zuschrift auf S. 4861 ff. magnetische Messungen vor, die belegen, dass die meisten Gastmolekule einen Ubergang des Netzwerks vom diamagnetischen Low-Spin- (rot) in den paramagnetischen High-Spin-Zustand (gelb) bewirken. Allein CS2 stabilisiert den Low-Spin-Zustand. Die induzierten Spinzustande werden auch nach Freisetzung der Gastspezies beibehalten.

Topological control in the hydrogen bond-directed self-assembly of ortho-, meta-, and para-phenylene-substituted dioxamic acid diethyl esters

[EN] The structures of the series of N,N¿-1,n-phenylenebis(oxamic acid ethyl ester) molecules with n = 2 (H2Et2opba, 1), 3 (H2Et2mpba, 2), and 4 (H2Et2ppba, 3) have been determined by single-crystal X-ray diffraction (XRD) methods. Density functional (DF) calculations have been performed on the simplest model system N-phenyloxamic acid methyl ester (HMepma). Compounds 1¿3 have either folded (H2Et2opba), bent (H2Et2mpba), or linear (H2Et2ppba) almost planar (periplanar) molecular configurations with the two oxalamide moieties being slightly tilted up and down, respectively, with respect to the benzene ring. The energy calculations as a function of the torsion angle (¿) around the N(amide)¿C(…

Structure and magnetic properties of a linear oximato-bridged tetranuclear copper(II) complex

Abstract The tetranuclear copper(II) complex of formula [Cu2(dmg)(Hdmg)(terpy)]2(ClO4)2 (1) (H2dmg = dimethylglyoxime and terpy = 2,2′:6′,2″-terpyridine) has been synthesized and its crystal structure determined by X-ray diffraction methods. It crystallizes in the triclinic system, space group P(−1), with a = 14.382(3), b = 13.728(3), c = 8.979(2) A, α = 96.99(2), β = 111.85(2), γ = 111.22(3)°, V = 1465.0(9) A3, Z = 1, Dc = 1.607 g cm−3, Mr = 1418.0, F(000) = 719, λ(Mo Kα) = 0.71073 A, μ(Mo Kα) = 16.61 cm−1 and T = 298 K. A total of 4891 reflections were measured over the range 2 ≤ θ ≤ 25° and 4393 of them were unique (I > 2.5σ(I) and used in the structural analysis. The structure of 1 may …

Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes.

The first catalytic enantioselective conjugate alkynylation of α,β-unsaturated 1,1,1-trifluoromethyl ketones has been carried out. Terminal alkynes and 1,3-diynes were treated with trifluoromethyl ketones in the presence of a low catalytic load of a CuI-MeOBIPHEP complex (2.5 mol %) and triethylamine (10 mol %) to give the corresponding trifluoromethyl ketones bearing a propargylic stereogenic center at the β position with good yields and excellent enantiomeric excesses in most of the cases. No 1,2-addition products were formed under the reaction conditions. The procedure showed broad substrate scope for alkyne, diyne, and enone. A rationale for the observed stereochemistry has been provide…

A Switchable Molecular Rotator: Neutron Spectroscopy Study on a Polymeric Spin-Crossover Compound

A quasielastic neutron scattering and solid-state 2H NMR spectroscopy study of the polymeric spin-crossover compound {Fe(pyrazine)[Pt(CN) 4]} shows that the switching of the rotation of a molecular fragment-the pyrazine ligand-occurs in association with the change of spin state. The rotation switching was examined on a wide time scale (10 -13-10 -3 s) by both techniques, which clearly demonstrated the combination between molecular rotation and spin-crossover transition under external stimuli (temperature and chemical). The pyrazine rings are seen to perform a 4-fold jump motion about the coordinating nitrogen axis in the high-spin state. In the low-spin state, however, the motion is suppres…

Thermo- and photo-modulation of exciplex fluorescence in a 3D spin crossover Hofmann-type coordination polymer

[EN] The search for bifunctional materials showing synergies between spin crossover (SCO) and luminescence has attracted substantial interest since they could be promising platforms for new switching electronic and optical technologies. In this context, we present the first three-dimensional Fe-II Hofmann-type coordination polymer exhibiting SCO properties and luminescence. The complex {Fe-II(bpben)[Au(CN)(2)]}@pyr (bpben = 1,4-bis(4-pyridyl)benzene) functionalized with pyrene (pyr) guests undergoes a cooperative multi-step SCO, which has been investigated by single crystal X-ray diffraction, single crystal UV-Vis absorption spectroscopy, and magnetic and calorimetric measurements. The resu…

Catalytic Asymmetric Formal [3+2] Cycloaddition of 2-Isocyanatomalonate Esters and Unsaturated Imines: Synthesis of Highly Substituted Chiral γ-Lactams.

[EN] Unlike their isocyano and isothiocyanato analogues, isocyanato esters remain almost unexplored as formal 1,3-dipoles in asymmetric catalytic reactions. The first asymmetric formal [3+2] cycloaddition involving isocyanato esters and electrophilic alkenes is reported. Diisopropyl 2-isocyanatomalonate reacts with a,b-unsaturated N-(o-anisidyl) imines in the presence of a Mg(OTf)2¿BOX complex to give highly substituted chiral pyrrolidinones featuring a conjugate exocyclic double bond with excellent yields and enantiomeric excesses up to 99%. Several transformations of the resulting heterocycles, including the synthesis of a pyroglutamic acid derivative, have been carried out.

Organocatalytic enantioselective functionalization of indoles in the carbocyclic ring with cyclic imines

[EN] An organocatalytic enantioselective functionalization in the carbocyclic ring of indoles with benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional organocatalyst. This aza-Friedel-Crafts reaction provides 4-indolyl, 5-indolyl and 7-indolyl sulfamidate derivatives in good yields (up to 99%) and with moderate to high enantioselectivities (up to 86% ee).

Organocatalytic enantioselective 1,6-aza-Michael addition of isoxazolin-5-ones to p-quinone methides

A thiourea-Brønsted base bifunctional catalyst allowed the enantioselective 1,6-aza-Michael addition of isoxazolin-5-ones to p-quinone methides to give isoxazolin-5-ones having a chiral diarylmethyl moiety attached to the N atom with fair to good yields and enantiomeric excesses. To the best of our knowledge this reaction represents the first example of enantioselective N-alkylation of isoxazolin-5-ones as well as the first example of enantioselective 1,6-aza-Michael reaction involving p-quinone methides.

Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to β,γ-unsaturated α-ketimino esters

[EN] In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from ß,gamma-unsaturated alfa-keto esters to give the corresponding chiral alfa,ß-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III) showed good activity and enantioselectivity, while Yb(III) provided the expected product with low yield and stereoselectivity, and the Sc(III) and In(III) complexes were completely inactive. The complex of La(OTf)3 with the diphenyl-pyBOX ligand prepared in situ provided the best results…

Synthesis and X-Ray Single Crystal Structure of Two New Copper Complexes with the Redox Active Ligand 1,10-Phenanthroline-5,6-dione

The synthesis and the crystal structures of the complexes [Cu(LI)2](ClO4) (1) and [Cu(LI)(CH3CN)2(ClO4)2] (2) are reported. 1 crystallizes in the monoclinic space group C2/c with the unit cell dimensions a = 13.169(4), b = 12.289(3), c = 14.732(3) A, β = 109.03(2)° and Z = 4. Copper(I) is coordinated to four N atoms of the two 1,10-Phenanthroline-5,6-dione (LI) ligands with a two-fold axis passing between the ligands. The copper(II) compound 2 crystallizes in the orthorhombic space group Pbn21 with unit cell dimensions of a = 7.498(5), b = 23.492(7), c = 12.363(4) A and Z = 4. Copper(II) coordination can be described as a distorted octahedron with the N donor atoms of one LI ligand and of t…

Highly enantioselective copper(I)-catalyzed conjugate addition of 1,3-diynes to a,b-unsaturated trifluoromethyl ketones

[EN] The conjugate diynylation of a,b-unsaturated trifluoromethyl ketones is carried out in the presence of a low catalytic load (2.5 mol%) of a copper(I)–MeOBIPHEP complex, triethylamine and a terminal 1,3-diyne. Pre-metalation of the terminal 1,3-diyne with stoichiometric or higher amounts of dialkylzinc reagent is not required. The corresponding internal diynes bearing a propargylic stereogenic center are obtained with good yields and excellent enantioselectivities.

Solid- and solution-state studies of the novel mu-dicyanamide-bridged dinuclear spin-crossover system {[(Fe(bztpen)]2[mu-N(CN)2]}(PF6)3 x n H2O.

The mononuclear diamagnetic compound {Fe(bztpen)[N(CN)2]} (PF6)CH3OH (1) (bztpen = N-benzyl-N,N′,N′- tris(2-pyridylmethyl)ethylenediamine) has been synthesized and its crystal structure studied. Complex 1 can be considered to be the formal pre-cursor of two new dinuclear, dicyanamide-bridged iron(II) complexes with the generic formula {[(Fe(bztpen)]2[μN(CN)2]}(PF6) 3·nH2O (n = 1 (2) or 0 (3)), which have been characterized in the solid state and in solution. In all three complexes, the iron atoms have a distorted [FeN6] octahedral coordination defined by a bztpen ligand and a terminal (1) or a bridging dicyanamide ligand (2 and 3). In the solid state, 2 and 3 can be considered to be molecu …

Regio-, Diastereo-, and Enantioselective Organocatalytic Addition of 4-Substituted Pyrazolones to Isatin-Derived Nitroalkenes

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Spin-crossover in the [Fe(abpt)2(NCX)2] (X=S, Se) system: Structural, Magnetic, calorimetric and photomagnetic studies

[EN] The compounds [Fe(abpt)(2)(NCS)(2)] (1) and [Fe(abpt)(2)(NCSe)(2)] (2) with abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole have been synthesized. The X-ray structures have been determined at 293 K. 1 and 2 are isostructural and crystallize in the monoclinic space group P2(1)/n with Z = 2, a = 8.538(8), b = 10.246(8), c = 16.45(2) Angstrom, beta = 93.98(9)degrees for 1 and a = 8.623(2), b = 10.243(3), c = 16.585(3) Angstrom, beta = 93.19(2)degrees for 2. In both complexes, the coordination core has a similar pseudo-octahedral geometry with the NCS- (1) and NCSe- (2) groups in the trans-position. Variable-temperature magnetic susceptibility data give evidence for a low-spin (LS)high…

Spin‐Crossover 2D Metal–Organic Frameworks with a Redox‐Active Ligand: [Fe(ttf‐adpy) 2 M(CN) 4 ]· n H 2 O (ttf‐adpy = 4‐Tetrathiafulvalenylcarboxamidopyridine; M II = Ni, Pd, Pt)

A new ttf (tetrathiofulvalene) ligand containing an amidopyridine moiety was synthesized and characterized. The electrochemical study of the 4-tetrathiofulvalenylcarboxamidopyridine (ttf–adpy) ligand showed two reversible oxidation processes at EI′1/2 = 0.08 V/Fc+–Fc and EII′1/2 = 0.26 V/Fc+–Fc. The crystal structure of [(ttf–adpyH)2Pt(CN)4] (1) was solved at 293 K, where 1 displays the triclinic space group P. The ttf–adpyH+ molecule is planar, and the bond lengths within the ttf core are in the usual range for neutral ttf moieties. The ttf–adpyH+ molecules and the [Pt(CN)4]2– anions organize in a three-dimensional network by means of hydrogen bonds and short S···S contacts. In the network…

Two-step spin crossover behaviour in the chiral one-dimensional coordination polymer [Fe(HAT)(NCS)2]∞

Solvated and unsolvated forms of the complex [Fe(HAT)(NCS)2]∞·(nMeOH) (1) (n = 1.5, 0; HAT = 1,4,5,8,9,12-hexaazatriphenylene) were prepared. The structure of 1·(1.5MeOH), measured at 120 K, showed that this system crystallizes in the homochiral P43 tetragonal space group. The solid is constituted of stacks of one-dimensional coordination polymers running along c-axis. All the FeII centres have the same Λ or Δ conformation and are in the LS state at 120 K. In the range of temperatures 10–300 K the magnetic properties of 1·(1.5MeOH) shows the occurrence of reversible spin crossover behaviour. However, above ca. 310 K complete desolvation of 1·(1.5MeOH) to give 1 was observed from crystal str…

ChemInform Abstract: Organocatalytic Enantioselective Alkylation of Pyrazol-3-ones with Isatin-Derived Ketimines: Stereocontrolled Construction of Vicinal Tetrasubstituted Stereocenters.

Financial support from the MINECO (Gobierno de Espana and FEDER (EU)) (CTQ2013-47949-P) and from Generalitat Valenciana (ISIC2012/001) is gratefully acknowledged. C. V. thanks MINECO for JdC contract. Access to NMR, MS and X-ray facilities from the Servei central de support a la investigacio experimental (SCSIE)-UV is also acknowledged.

Spin crossover in a catenane supramolecular system.

The compound [Fe(tvp)(2)(NCS)(2)] . CH(3)OH, where tvp is 1,2-di-(4-pyridyl)-ethylene, has been synthesized and characterized by x-ray single-crystal diffraction. It consists of two perpendicular, two-dimensional networks organized in parallel stacks of sheets made up of edge-shared [Fe(II)](4) rhombuses. The fully interlocked networks define large square channels in the [001] direction. Variable-temperature magnetic susceptibility measurements and Mossbauer studies reveal that this compound shows low-spin to high-spin crossover behavior in the temperature range from 100 to 250 kelvin. The combined structural and magnetic characterization of this kind of compound is fundamental for the inte…

ChemInform Abstract: E,Z-Stereodivergent Synthesis of N-Tosyl α,β-Dehydroamino Esters via a Mukaiyama-Michael Addition

The stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama–Michael addition is reported. The reaction of silylketene acetals with N-tosylimines derived from β,γ-unsaturated α-keto esters in dichloromethane provided the corresponding (Z)-α,β-dehydroamino esters while the (E)-isomers were obtained when the reaction was carried out in the presence of 10 mol% copper(II) triflate.

Organocatalytic Enantioselective Friedel–Crafts Aminoalkylation of Indoles in the Carbocyclic Ring

The first general catalytic method for the, so far elusive, enantioselective Friedel−Crafts functionalization of indoles in the carbocyclic ring is presented. This transformation contrasts with the usual tendency of these heterocycles to react at the azole ring. For this purpose, the four regioisomeric hydroxy carbocyclic-substituted indoles were reacted with several isatinderived ketimines, using a Cinchona alkaloid-based squaramide, in a low 0.5−5 mol % catalyst loading, as a bifunctional catalyst. This methodology allows the functionalization of indoles in every position of the carbocyclic ring in a regio- and enantioselective fashion, by switching only the position of the hydroxy group …

ChemInform Abstract: Organocatalytic Enantioselective Aza-Friedel-Crafts Reaction of 2-Naphthols with Benzoxathiazine 2,2-Dioxides.

An organocatalytic enantioselective aza-Friedel–Crafts addition of 2-naphthols to benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional catalyst. The method allows the use of a wide range of aromatic compounds as nucleophiles, including 1-naphthol and sesamol, and benzoxathiazines 2,2-dioxides, expanding the existing state of the art enantioselective synthesis of aminomethylnaphthol derivatives.

Synthesis, crystal structure, thermal and magnetic properties of [Mn(H2O)6][Cu(pdta).2H2O (pdta= 1,3-propylenediamine-N,N,N',N'-tetraacetate

[EN] On mixing concentrated aqueous solutions of pdta, Cu(II) and Mn(II) in the ratio 1:1:1 at pH 4.5, single crystals of the complex [Mn(H2O)6][Cu(pdta)]·2H2O (1) (pdta=1,3-propylenediamine-N,N,N'N'-tetraacetate) were obtained. X-ray structural analysis revealed that in the anion [Cu(pdta)]2- the coordination polyhedron around the Cu(II) ion can be described as a tetragonaly distorted CuN2O4 octahedron, whereas the cation [Mn(H2O)6]2+ can be described as a very regular MnO6 octahedron. Thermogravimetric analysis shows that at 110°C compound 1 loses its eight water molecules yielding the anhydrous compound [MnCu(pdta)] (2). Variable-temperature magnetic susceptibility measurements indicate …

Chemistry and reactivity of dinuclear manganese oxamate complexes: Aerobic catechol oxidation catalyzed by high-valent bis(oxo)-bridged dimanganese(IV) complexes with a homologous series of binucleating 4,5-disubstituted-o-phennylenedioxamate ligands

[EN] The high-valent bis(oxo)-bridged dimanganese(IV) complexes with the series of binucleating 4.5-X-2-o-phenylenebis(oxamate) ligands (opbaX(2); X = H, Cl, Me) (1a-c) have been synthesized and characterized structurally, spectroscopically and magnetically. Complexes la-c possess unique Mn-2(mu-O)(2) core structures with two o-phenylenediamidate type additional bridges which lead to exceptionally short Mn-Mn distances (2.63-2.65 angstrom) and fairly bent Mn-O-Mn angles (94.1 degrees-94.6 degrees). The cyclovoltammograms of la-c in acetonitrile (25 degrees C, 0.1 M Bu4NPF6) show an irreversible one-electron oxidation peak at moderately high anodic potentials (E-ap = 0.50-0.85 V versus SCE),…

ChemInform Abstract: Catalytic Enantioselective Conjugate Alkynylation of α,β-Unsaturated 1,1,1-Trifluoromethyl Ketones with Terminal Alkynes.

Financial support (Grant CTQ2013-47494-P) from the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana). A.S.M. thanks the MINECO for a predoctoral grant (FPI program). Access to NMR and MS facilities from the Servei Central de Suport a la Investigacio Experimental (SCSIE)-UV is also acknowledged.

Organocatalytic Enantioselective Friedel-Crafts Alkylation of 1-Naphthol Derivatives and Activated Phenols with Ethyl Trifluoropyruvate

An organocatalytic enantioselective Friedel–Crafts alkylation of a series of substituted 1- naphthol derivatives and activated phenols with ethyl trifluoropyruvate, catalyzed by a quinine-derived squaramide, is presented. Good yields and high to excellent enantioselectivities of the Friedel– Crafts alkylation products were obtained.

Assembly and encapsulation of coordination tectons driven by hydrogen-bondingand space-filling

[FR] Le composé ¿Fe(LI)3¿2¿Fe(H2O)6¿(ClO4)6 (2), LI = 1,10-phénanthroline-5,6-dione, a été synthétisé et caractérisé. La structure cristalline 2 est définie par un assemblage bidimensionnel non covalent, peu commun, constitué par des tectons chiraux ¿Fe(LI)3¿2+, assemblés par des cations ¿Fe(H2O)6¿2+ encapsulés dans des cages. Ces cages sont formées par 12 liaisons hydrogène établies entre les molécules d¿eau coordinées et les groupes dione appartenant à six molecules chirales ¿Fe(LI)3¿2+ ¿, ¿ alternées.

Organocatalytic Enantioselective Aminoalkylation of 5‐Aminopyrazole Derivatives with Cyclic Imines

The first enantioselective alkylation of 5‐aminopyrazoles is described with good results. The organocatalytic alkylation of 5‐aminopyrazoles have been accomplished using benzoxathiazine 2,2‐dioxides as electrophiles and a bifunctional squaramide organocatalyst.

Epitaxial Thin-Film vs Single Crystal Growth of 2D Hofmann-Type Iron(II) Materials: A Comparative Assessment of their Bi-Stable Spin Crossover Properties

Integration of the ON-OFF cooperative spin crossover (SCO) properties of FeII coordination polymers as components of electronic and/or spintronic devices is currently an area of great interest for potential applications. This requires the selection and growth of thin films of the appropriate material onto selected substrates. In this context, two new series of cooperative SCO two-dimensional FeII coordination polymers of the Hofmann-type formulated {FeII(Pym)2[MII(CN)4]·xH2O}n and {FeII(Isoq)2[MII(CN)4]}n (Pym = pyrimidine, Isoq = isoquinoline; MII = Ni, Pd, Pt) have been synthesized, characterized, and the corresponding Pt derivatives selected for fabrication of thin films by liquid-phase …

Two- and one-step cooperative spin transitions in Hofmann-like clathrates with enhanced loading capacity

Structural, magnetic, calorimetric and Mo¨ssbauer studies of the cooperative spin crossover naphthalene and nitrobenzene clathrates of the novel FeII Hofmann-like porous metal–organic framework {Fe(bpb)[Pt(CN)4]}2Guest are described (bpb = bis(4-pyridyl)butadiyne).

E,Z-Stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama-Michael addition

The stereodivergent synthesis of N-tosyl α,β-dehydroamino esters via a Mukaiyama–Michael addition is reported. The reaction of silylketene acetals with N-tosylimines derived from β,γ-unsaturated α-keto esters in dichloromethane provided the corresponding (Z)-α,β-dehydroamino esters while the (E)-isomers were obtained when the reaction was carried out in the presence of 10 mol% copper(II) triflate.

Switchable Spin-Crossover Hofmann-Type 3D Coordination Polymers Based on Tri- and Tetratopic Ligands

[EN] Fe-II spin-crossover (SCO) coordination polymers of the Hofmann type have become an archetypal class of responsive materials. Almost invariably, the construction of their architectures has been based on the use of monotopic and linear ditopic pyridine like ligands. In the search for new Hofmann-type architectures with SCO properties, here we analyze the possibilities of bridging ligands with higher connectivity degree. More precisely, the synthesis and structure of {Fe-II(L-N3)[M-I(CN)(2)](2)}center dot(Guest) (Guest = nitro-benzene, benzonitrile, o-dichlorobenzene; M-I = Ag, Au) and {Fe-II(L-N4)[Ag-2(CN)(3)][Ag(CN)(2)]}center dot H2O are described, where L-N3 and L-N4 are the tritopic…

Enantioselective LaIII-pyBOX-Catalyzed Nitro-Michael Addition to (E)-2-Azachalcones

A [La(OTf)3] complex with a new pyBOX ligand bearing a bulky 1-naphthylmethyl substituent at the 4′-position of the oxazoline ring catalyzes the conjugate addition of nitroalkanes to a broad range of (E)-2-azachalcones, providing the expected nitro-Michael products with good yields and enantiomeric excesses up to 87 %. The optical purity of the products can be increased by a single crystallization. A plausible stereochemical model to account for the observed stereochemistry has been proposed.

Copper-catalysed enantioselective Michael addition of malonic esters to β-trifluoromethyl-α,β-unsaturated imines

[EN] Copper triflate-BOX complexes catalyse the enantioselective conjugate addition of methyl malonate to beta-trifluoromethyl-alpha,beta-unsaturated imines to give the corresponding enamines bearing a trifluoromethylated stereogenic centre with good yields, and diastereo- and enantioselectivities. The usefulness of the method has been shown with the synthesis of optically active beta-trifluoromethyl delta-amino esters and optically active trifluoromethyl piperidones.

Enantioselective Addition of Nitromethane to 2-Acylpyridine N-Oxides. Expanding the Generation of Quaternary Stereocenters with the Henry Reaction

[EN] The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or alpha-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.

Spin Crossover in a Series of Non-Hofmann-Type Fe(II) Coordination Polymers Based on [Hg(SeCN)3]− or [Hg(SeCN)4]2– Building Blocks

Self-assembly of [Hg(SeCN)4]2- tetrahedral building blocks, iron(II) ions, and a series of bis-monodentate pyridyl-type bridging ligands has afforded the new heterobimetallic HgII-FeII coordination polymers {Fe[Hg(SeCN)3]2(4,4'-bipy)2}n (1), {Fe[Hg(SeCN)4](tvp)}n (2), {Fe[Hg(SeCN)3]2(4,4'-azpy)2}n (3), {Fe[Hg(SeCN)4](4,4'-azpy)(MeOH)}n (4), {Fe[Hg(SeCN)4](3,3'-bipy)}n (5) and {Fe[Hg(SeCN)4](3,3'-azpy)}n (6) (4,4-bipy = 4,4'-bipyridine, tvp = trans-1,2-bis(4-pyridyl)ethylene, 4,4'-azpy = 4,4'-azobispyridine, 3,3-bipy = 3,3'-bipyridine, 3,3'-azpy = 3,3'-azobispyridine). Single-crystal X-ray analyses show that compounds 1 and 3 display a two-dimensional robust sheet structure made up of infini…

Synthesis, crystal structures, and solid state quadratic nonlinear optical properties of a series of stilbazolium cations combined with gold cyanide counter-ion

Three salts built up from (E)-4′-(dimethylamino)-stilbazolium (DMAS)H+, (E)-4′-(diethylamino)-stilbazolium (DEAS)H+, (E)-4′-{2-(methoxymethyl) pyrrolidinyl}-stilbazolium (MPS)H+, and gold cyanide as a counter-ion, are reported. The crystal structures have been solved for (DEAS)H+ Au(CN)2− (Cc space group), and for (MPS)H+ Au(CN)2− (P1 space group). The semi-empirical (ZINDO) calculated static hyperpolarizability (β0) of (MPS)H+ is equal to 147 × 10−30 cm5esu−1, in solid state, which is 25% higher than that of the cation of the well known (E)-4′-(dimethylamino)-methylstilbazolium tosylate (DAST). (MPS)H+ Au(CN)2− exhibits a unique crystal structure in which the cations are perfectly aligned.…

Bidirectional Chemo-Switching of Spin State in a Microporous Framework

The ins and outs of spin: Using the microporous coordination polymer {Fe(pz)[Pt(CN)(4)]} (1, pz=pyrazine), incorporating spin-crossover subunits, two-directional magnetic chemo-switching is achieved at room temperature. In situ magnetic measurements following guest vapor injection show that most guest molecules transform 1 from the low-spin (LS) state to the high-spin (HS) state, whereas CS(2) uniquely causes the reverse HS-to-LS transition.

Synthese, Struktur und magnetische Eigenschaften eines achtkernigen Nickel(II)-Komplexes mit einer zentralenhexahedro-Ni8-Einheit

Heterobimetallic MOFs containing tetrathiocyanometallate building blocks: Pressure-induced spin crossover in the porous {Fe II(pz)[Pd II(SCN) 4]} 3D coordination polymer

Here we describe the synthesis, structure, and magnetic properties of two related coordination polymers made up of self-assembling Fe(II) ions, pyrazine (pz), and the tetrathiocyanopalladate anion. Compound {Fe(MeOH) 2[Pd(SCN) 4]}·pz (1a) is a two-dimensional coordination polymer where the Fe(II) ions are equatorially coordinated by the nitrogen atoms of four [Pd(SCN) 4] 2- anions, each of which connects four Fe(II) ions, forming corrugated layers {Fe[Pd(SCN) 4]} ∞. The coordination sphere of Fe(II) is completed by the oxygen atoms of two CH 3OH molecules. The layers stack one on top of each other in such a way that the included pz molecule establishes strong hydrogen bonds with the coordin…

Synergetic effect of host-guest chemistry and spin crossover in 3D Hofmann-like metal-organic frameworks [Fe(bpac)M(CN)4] (M=Pt, Pd, Ni).

The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN) 4] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN) 4]} n planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, w…

New Sesquiterpene Lactones and Other Constituents fromCentaurea paui

Aerial parts of Centaurea paui afforded, in addition to several known sesquiterpene lactones, the two new elemanolides 2–4, the new elemane derivative 5 as well as the five new heliangolides 14–18. Their structures were elucidated by spectroscopic methods, especially high-field NMR spectroscopy. The structure of the heliangolide 12 previously isolated from this plant, has been confirmed by X-ray diffraction.

ChemInform Abstract: Organocatalytic Enantioselective Synthesis of Pyrazoles Bearing a Quaternary Stereocenter.

An efficient one-pot asymmetric synthesis of pyrazoles bearing a chiral quaternary stereocenter has been developed. Quinine-derived thiourea catalyzed the enantioselective addition of pyrazolones to isatin-derived ketimines, providing the corresponding acetylated pyrazoles after in situ treatment with Ac2 O/Et3 N. The corresponding pyrazoles were afforded in high yields and excellent enantioselectivities.

Sublimable complexes with spin switching: chemical design, processing as thin films and integration in graphene-based devices

Among the different types of switchable molecular compounds, sublimable Fe(II) SCO molecules provide a suitable platform to develop smart devices that respond to external stimuli. Here we report the synthesis, crystallographic structure and magnetic properties of three new neutral Fe(II) SCO molecules belonging to the {Fe[H2B(pz)2]2(L)} family with bidentate-alpha-diimine ligands L = 3-(pyridin-2-yl)-[1,2,3]triazolo[1,5-a]pyridine (tzpy), 5,5,6,6-tetrahydro-4H,4H-2,2-bi(1,3-thiazine) (btz) and 4,4,5,5-tetrahydro-2,2-bithiazole (bt) (1, 2 and 3, respectively), as well as two solvated forms of 1 and 3. All three desolvated compounds present thermal- and light-induced SCO transitions with diff…

Enantioselective Synthesis of Tertiary Alcohols through a Zirconium-Catalized Friedel-Crafts Alkylation of Pyrroles with alpha-Ketoesters

Chiral complexes of 1,10-bi-2-naphthol-based ligands with zirconium tert-butoxide catalyze the Friedel Crafts alkylation of pyrroles with R-ketoesters to afford tertiary alcohols in good yields and ee up to 98%. The reaction is also of application to 4,7-dihydroindole to give C2-alkylated indoles after oxidation with p-benzoquinone.

From six-coordinate to eight-coordinate iron(ii) complexes with pyridyltriazolo-pyridine frameworks

A new octacoordinated Fe(II) compound, [FeII(LN4)2](BPh4)2·3CH2Cl2, as an example of the scarce FeN8 systems, has been isolated with a tetradentate triazolopyridine-based ligand from a solution containing the related hexacoordinated [FeII(LN3)2]2+ complex, with LN3 = pyridyltriazolo-pyridyl-bromopyrimidine and LN4 = bis(pyridyltriazolo-pyridine).

ChemInform Abstract: Synthesis of Functionalized Indoles with an α-Stereogenic Ketone Moiety Through an Enantioselective Friedel-Crafts Alkylation with (E)-1,4-Diaryl-2-butene-1,4-diones.

Chiral complexes of BINOL-based ligands with hafnium tert-butoxide catalyze the enantioselective Friedel-Crafts alkylation of indoles with (E)-1,4-diaryl-2-butene-1,4-diones at room temperature, with good yields and ee up to 94%. Hafnium(IV) was found to be a more effective Lewis acid than other frequently used metal ions such as titanium(IV) or zirconium(IV). Unlike the enantioselective Friedel-Crafts alkylation of indoles with α,β-unsaturated compounds where the stereogenic center is generated in the β-position to a carbonyl group, the Friedel-Crafts alkylation with 2-butene-1,4-diones described here generates an α-stereogenic center with respect to one of the carbonyl groups. This can be…

Organocatalytic enantioselective aminoalkylation of pyrazol-3-ones with aldimines generated in situ from α-amido sulfones

Herein, an efficient asymmetric aminoalkylation of pyrazolones with α-amido sulfones catalyzed by a quinine-derived squaramide in dichloromethane/aqueous media has been established. A variety of chiral amines were obtained with high yields (up to 98%) and excellent enantioselectivities (up to 99% ee). The corresponding products are transformed into optically active acetylated pyrazoles after treatment with Ac2O/Et3N, because of the instability of some adducts. The reaction tolerates a wide range of α-amido sulfones and different pyrazolones.

ChemInform Abstract: Highly Enantio- and Diastereoselective Inverse Electron Demand Hetero-Diels-Alder Reaction Using 2-Alkenoylpyridine N-Oxides as Oxo-Heterodienes.

A general catalytic inverse electron demand hetero-Diels Alder reaction for 2-alkenoylpyridine N-oxides is presented. 2-Alkenoylpyridine N-oxides react very efficiently with alkenes in the presence of bisoxazolidine-copper(II) [BOX-Cu(II)] complexes to give chiral dihydropyrans bearing a pyridine ring at the 6-position with very high yields and excellent diastereo- and enantioselectivity. These heterodienes exhibited higher reactivity and enantioselectivity than the corresponding non-oxidized 2-alkenoylpyridines.

Organocatalytic Enantioselective Alkylation of Pyrazol-3-ones with Isatin-Derived Ketimines: Stereocontrolled Construction of Vicinal Tetrasubstituted Stereocenters

A quinine-derived thiourea catalysed the enantioselective addition of 4-substituted pyrazolones to isatin-derived ketimines, providing a variety of aminooxindole-pyrazolone adducts containing congested vicinal tetrasubstituted stereocentres with excellent outcomes (up to 98% yield, >20:1 dr and 98% ee).

Thermal-,Pressure-, and Light-Induced Spin Transition in Novel Cyanide-Bridged FeII-AgI Bimetallic Compounds with Three-Dimensional Interpenetrating Double Structures {FeIILx[Ag(CN)2]2}·G

[EN] Low-spin, high-spin and spin-transition behaviours have been observed for the doubly interpenetrating three-dimensional bimetallic compounds {Fe-II(pz)[Ag(CN)(2)](2)}.pz (pz= pyrazine), {Fe-II(4,4'-bipy)(2)[Ag(CN)(2)](2)} (4,4'-bipy-4,4'-bipyridine), and {Fe-II-(bpe)(2)[Ag(CN)(2)](2)} (bpe = bispyridylethylene), respectively. The single crystals of the bpe derivative undergo a spin transition with a large hysteresis loop at about 95 K. After several warming and cooling cycles, the single crystals become a microcrystalline powder with 50% spin transition. Influence of pressure- as well as light-induced excited spin-state trapping (LIESST) on the thermal 50% spin transition of the microc…

Catalytic enantioselective aza-Reformatsky reaction with seven-membered cyclic imines dibenzo[b,f][1,4]oxazepines

A catalytic enantioselective aza-Reformatsky reaction is reported with cyclic dibenzo[b,f][1,4]oxazepines and ethyl iodoacetate leading to the synthesis of chiral ethyl 2-(10,11-dihydrodibenzo[b,f][1,4]oxazepin-11-yl)acetate derivatives with excellent yields and high enantioselectivities (up to 98% yield and 97 : 3 er) using a readily available diaryl prolinol L4 as the chiral ligand and Me2Zn as the zinc source under an air atmosphere. Furthermore, different transformations were carried out with the corresponding chiral β-amino esters, preserving in all cases the optical purity.

Cooperative Spin Transition in the Two-Dimensional Coordination Polymer [Fe(4,4′-bipyridine)2(NCX)2]·4CHCl3 (X = S, Se)

Two new isostructural two-dimensional (2D) coordination polymers exhibiting spin crossover (SCO) behavior of formulation [Fe(4,4'-bipy)(2)(NCX)(2)]·4CHCl(3) (4,4'-bipy = 4,4'-bipyridine; X = S [1·4CHCl(3)], Se [2·4CHCl(3)]) have been synthesized and characterized, and both undergo cooperative spin transitions (ST). For 1·4CHCl(3) the ST takes place in two steps with critical temperatures of T(c1)(down) = 143.1 K, T(c2)(down) = 91.2 K, T(c1)(up) = 150.7 K, and T(c2)(up) = 112.2 K. 2·4CHCl(3) displays half ST characterized by T(c)(down) = 161.7 K and T(c)(up) = 168.3 K. The average enthalpy and entropy variations and cooperativity parameters associated with the ST have been estimated to be ΔH…

Spin crossover in six-coordinate [Fe(L)2(NCX)2] compounds with L = DPQ = 2,3-bis-(2′-pyridyl)-quinoxaline, ABPT = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole and X = S, Se: synthesis, magnetic properties and single crystal studies

[EN] The iron(II) compounds of formulae [Fe(DPQ)2(NCS)2]·CO(CH)3)2(DPQ = 2,3-bis-(2¿-pyridyl)-quinoxaline) (1) and [Fe(ABPT)2-(NCX)2] (ABPT = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole) X = S (2) and Se (3) were synthesized and the crystal structure of 1 determined by X-ray diffraction methods. It crystallizes in the monoclinic system . The structure is made up of discrete [Fe(DPQ)2(NCS)2] units. Each metal atom is in a distorted FeN6 octahedral environment, the Fe¿N bonds ranging from 2.013(8) Å to 2.425(8) Å. Variable-temperature magnetic susceptibility data in the temperature range 290¿4.2 K revealed that 1 is high spin, in contrast to 2 and 3 which show a moderately cooperative high s…

Organocatalytic Enantioselective 1,6-aza -Michael Addition of Isoxazolin-5-ones to p -Quinone Methides

Study of the interaction between [Cu(bipy)]2+ and oxalate in dimethyl sulfoxide. Crystal structure of [Cu2(bipy)2(H2O)2ox]SO4·[Cu(bipy)ox]

Abstract A study of complex formation between [Cu(bipy)]2+ and ox2− (bipy and ox2− being 2,2′-bipyridyl and the dianion of oxalic acid), has been carried out by potentiometry in dimethyl sulfoxide solution. The constants of the equilibria and are log β110 = 11.165(1) and log β210 = 13.185(5) at 25 °C and 0.1 mol dm−3 tetra-n- butylammonium perchlorate. The high values of these constants are consistent with the symmetrical bidentate and bis-bidentate modes of oxalate in [Cu(bipy)ox] and [Cu2(bipy)2ox]2+ units, respectively, as shown by X-ray diffraction studies. Well-formed single crystals of [Cu2(bipy)2(H2O)2ox]SO4· [Cu(bipy)ox] were grown from aqueous solutions and characterized by X-ray d…

Homoleptic iron(II) complexes with the ionogenic ligand 6,6′-Bis(1H-tetrazol-5-yl)-2,2′-bipyridine: spin crossover behavior in a singular 2D spin crossover coordination polymer

Deprotonation of the ionogenic tetradentate ligand 6,6′-bis(1H-tetrazol-5-yl)-2,2′-bipyridine [H2bipy(ttr)2] in the presence of FeII in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2]− and [bipy(ttr)2]2– embrace the FeII centers defining discrete molecular units 1 with the FeII ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the FeII is high-spin, and its Mössbauer spectrum is characteriz…

Spin crossover star-shaped metallomesogens of iron(II).

Three new types of spin crossover (SCO) metallomesogens of Fe-II based on symmetric tripod ligands and their magnetic and structural properties are reported here. These were obtained by condensation of tris(2-aminoethyl)-amin (tren) with the aldehyde derived from 3-alkoxy-6-methylpyridine (mpyN, N (number of carbon atoms in n-alkyl chains) = 8, 18), 1-alkyl-1H-imidazole (imN, N = 4, 16, 18, 20, 22), or 1-alkyl-1H-benzimidazole (bimN, N = 6, 14, 16, 18, 20). A complex derived from 1-octadecyl-1H-naphtho[2,3-d]imidazole (nim18) retains the high spin state at any temperature. Single crystals of the short-chain complexes were investigated by a combination of X-ray crystallography, magnetic meas…

Nanoporosity, Inclusion Chemistry, and Spin Crossover in Orthogonally Interlocked Two-Dimensional Metal-Organic Frameworks

[Fe(tvp)(2)(NCS)(2)] (1) (tvp=trans-(4,4-vinylenedipyridine)) consists of two independent perpendicular stacks of mutually interpenetrated two-dimensional grids. This uncommon supramolecular conformation defines square-sectional nanochannels (diagonal approximate to 2.2nm) in which inclusion molecules are located. The guest-loaded framework 1@guest displays complete thermal spin-crossover (SCO) behavior with the characteristic temperature T-1/2 dependent on the guest molecule, whereas the guest-free species 1 is paramagnetic whatever the temperature. For the benzene-guest derivatives, the characteristic SCO temperature T-1/2 decreases as the Hammet sigma(p) parameter increases. In general, …

Crystalline-state reaction with allosteric effect in spin-crossover, interpenetrated networks with magnetic and optical bistability.

A net change: A fully reversible ligand substitution involving coordination/ uncoordination of gaseous water and pyrimidine induces the repetitive allosteric transformation of three interpenetrated nets into a single three-dimensional net. The transformation does not affect the crystallinity of the sample but alters significantly the spin-crossover transition; the compound shows magnetic and chromatic bistability (see picture).

Meltable Spin Transition Molecular Materials with Tunable Tc and Hysteresis Loop Width.

Herein, we report a way to achieve abrupt high-spin to low-spin transition with controllable transition temperature and hysteresis width, relying not on solid-state cooperative interactions, but utilizing coherency between phase and spin transitions in neutral FeII meltable complexes

Polymorphism and Pressure Driven Thermal Spin Crossover Phenomenon in [Fe(abpt)2(NCX)2] (X=S, and Se): Synthesis,Structure and Magnetic Properties

The monomeric compounds [Fe(abpt 2(NCX)2(X = S (1), Se (2) and abpt = 4-amino- 3,5-bis(pyridin-2-yl)-1,2,4-triazole) have been synthesized and characterized. They crystallize in the monoclinic P21/n space group with a = 11.637(2) A, b = 9.8021(14) A, c = 12.9838(12) A, β = 101.126(14)°, and Z=2 for 1, and a= 11.601(2) A, b = 9.6666(14) A, c = 12.883(2) A, β = 101.449(10)°, and Z = 2 for 2. The unit cell contains a pair mononuclear [Fe(abpt)2(NCX)21 units related by a center of symmetry. Each iron atom, located at a molecular inversion center, is in a distorted octahedral environment. Four of the six nitrogen atoms coordinated to the Fe(II) ion belong to the pyridine-N(1) and triazole-N(2) r…

Control of the spin state by charge and ligand substitution: two-step spin crossover behaviour in a novel neutral iron(II) complex

The influence of the charge and steric hindrance on the spin state of a series of four monomeric Fe-II complexes derived from the tridentate tigands 2-(1H-benzoimidazol-2-yl)-1,10-phenanthroline (Hphenbi) and 2-(1H-benzoimidazol-2-yl-9-methyl-1,10-phenanthroline (Hmphenbi) and their deprotonated forms (phenbi(-), mphenbi(-)) are investigated. The crystal structure and magnetic properties show that [Fe(Hphenbi)(2)](BF4)(2)center dot 1.5C(6)H(5)NO(2)center dot H2O (1) and its neutral form [Fe(phenbi)(2)]center dot 2CHCl(3)center dot H2O (2) are low-spin complexes at 400 K due to the strong ligand field imparted by the terpyridine-like tigand. In contrast, the steric hindrance induced by the m…

Pressure Effect Studies on the 3D Spin Crossover System: {Fe(3CN-py)2[M(CN)2]2}·nH2O (n < 2/3, M = Ag(I), Au(I))

[EN] Pressure effect investigations on the magnetic behaviour of the 3D SCO polymers {Fe(3CN-py)2[Ag(CN)2]2} · 2/3H2O (1) and {Fe(3CN-py)2[Au(CN)2]2} · 2/3H2O (2) have been carried out in the range of 105 Pa to 0.7 GPa. Despite both compounds are isostructural their magnetic behaviour under applied hydrostatic pressures is very different. Strong nonlinearity in the Tc(P) vs. P plot has been observed for compound 1 a fact which contrasts with the almost linear dependence observed for each spin transition in 2. However, both compounds are extremely sensitive to the application of pressure as well as the Tc(P) vs. P plots denote.

Synthesis and Characterisation of a New Series of Bistable Iron(II) Spin-Crossover 2D Metal-Organic Frameworks

Twelve coordination polymers with formula {Fe(3-Xpy)(2)[M(II)(CN)(4)]} (M(II): Ni, Pd, Pt; X: F, Cl, Br, I; py: pyridine) have been synthesised, and their crystal structures have been determined by single-crystal or powder X-ray analysis. All of the fluoro and iodo compounds, as well as the chloro derivative in which M(II) is Pt, crystallise in the monoclinic C2/m space group, whereas the rest of the chloro and all of the bromo derivatives crystallise in the orthorhombic Pnc2 space group. In all cases, the iron(II) atom resides in a pseudo-octahedral [FeN(6)] coordination core, with similar bond lengths and angles in the various derivatives. The major difference between the two kinds of str…

Polymorphism and “reverse” spin transition in the spin crossover system [Co(4-terpyridone)2](CF3SO3)2·1H2O

[EN] Compound [Co(4-terpyridone)(2)](CF3SO3)(2)center dot 1H(2)O, where 4-terpyridone is 2,6-bis(2-pyridyl)-4(1H)-pyridone, forms two polymorphs. Polymorph 1 displays a continuous spin conversion in the temperature region 300-120 K while polymorph 2 shows, on cooling, the onset of a continuous high-spin (HS) to low-spin (LS) conversion interrupted by an abrupt "reverse'' spin transition in the temperature region 217-203 K. The formed unstable HS intermediate phase (IP) undergoes a strong cooperative "normal'' spin transition characterised by a hysteresis loop 33 K wide. The structural data give support for a crystallographic phase transition, which takes place concomitantly with the "revers…

Guest Modulation of Spin-Crossover Transition Temperature in a Porous Iron(II) Metal Organic Framework: Experimental and Periodic DFT Studies

The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin-crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)(4)]} (1) with five-membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin-crossover transition with hysteresis loops 14-29 K wide and average critical temperatures T-c=201 K (1.fur), 167 K (1.pyr), and 114.6 K (1.thio) well below that of the parent compound 1 (T-c=295 K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1.fur, while 1.pyr and 1.thio show 50% spin transition. For 1.fur the transformation between the HS and IS (mi…

Cover Feature: Cyanido‐Bridged Fe II –M I Dimetallic Hofmann‐Like Spin‐Crossover Coordination Polymers Based on 2,6‐Naphthyridine (Eur. J. Inorg. Chem. 3‐4/2018)

Synthesis, crystal structure and magnetic properties of the spin crossover system [Fe(pq)3]2+

Abstract Three new compounds formulated (ClO4)2[Fe(pq)3] (1), (BF4)2[Fe(pq)3] · EtOH (2) and {(ClO4)[MnCr(C2O4)3][Fe(pq)2(H2O)2]} (3), where pq is 2,2′-pyridylquinoline, have been synthesised and characterised. Despite the different crystal packing exhibited by 1 and 2, the cationic species [Fe(pq)3]2+ are structurally quite similar. At 293 K, the Fe–N bond lengths are characteristic of the iron(II) in the high-spin state. In contrast to 1, 2 undergoes a continuous spin transition. Indeed, at 95 K its structure experiences a noticeable change in the Fe–N bonds and angles, i.e. the Fe–N bonds shorten by 0.194 A on the average. The magnetic behaviour confirms that 1 is fully high-spin in the …

Thermal and pressure-induced spin crossover in a novel three-dimensional Hoffman-like clathrate complex

The synthesis and crystal structure of the interpenetrated metal–organic framework material Fe(bpac)2[Ag(CN)2]2 (bpac = 4,4′-bis(pyridyl)acetylene) are reported along with the characterization of its spin crossover properties by variable temperature magnetometry and Mossbauer spectroscopy. The complex presents an incomplete stepped spin transition as a function of temperature that is modified upon successive thermal cycling. The pressure-induced transition has also been investigated by means of high pressure Raman spectroscopy using a diamond anvil cell. The results show that it is possible to reach the thermally-inaccessible fully low spin state at room temperature by applying hydrostatic …

ChemInform Abstract: Enantioselective Synthesis of Tertiary Alcohols Through a Zirconium-Catalyzed Friedel-Crafts Alkylation of Pyrroles with α-Ketoesters.

Chiral complexes of 1,1′-bi-2-naphthol-based ligands with zirconium tert-butoxide catalyze the Friedel–Crafts alkylation of pyrroles with α-ketoesters to afford tertiary alcohols in good yields and ee up to 98%. The reaction is also of application to 4,7-dihydroindole to give C2-alkylated indoles after oxidation with p-benzoquinone.

[Fe III (bztpen)(OCH 3 )](PF 6 ) 2 : Stable Methoxide–Iron(III) Complex Exhibiting Spin Crossover Behavior in the Solid State

Complex [Fe III (bztpen)(OCH 3 )](PF 6 ) 2 (1) crystallizes as the major yellow-brown product from spontaneous oxidation of its corresponding iron(II) counterpart in methanol solution. Magnetic measurements and EPR spectra demonstrate that 1 undergoes a poorly cooperative 6 A 1 ↔ 2 T 2 spin conversion in the temperature range 300-50 K, with characteristic thermodynamic parameters ΔH = 6.15 kJ mol -1 , ΔS = 39.88 J K -1 mol -1 , and T 1/2 = 154 K. The crystal structure of 1 has been investigated at 100 and 293 K.

Enantioselective addition of sodium bisulfite to nitroalkenes. A convenient approach to chiral sulfonic acids

An enantioselective organocatalytic addition of sodium bisulfite to (E)-nitroalkenes has been developed by using a chiral bifunctional organocatalyst. The present methodology provides a variety of chiral β-nitroethanesulfonic acid compounds (17 examples) with excellent results: up to 99% yield and excellent enantioselectivity (up to 96% ee). The reaction tolerates (hetero)aryl and alkyl substituents on the β-nitroalkenes, and β,β-disubstituted nitroalkenes.

Cyanido-Bridged FeII-MI Dimetallic Hofmann-Like Spin-Crossover Coordination Polymers Based on 2,6-Naphthyridine

[EN] Two new 3D spin-crossover (SCO) Hofmann-type coordination polymers {Fe(2,6-naphthy)[Ag(CN)2][Ag2(CN)3]} (1; 2,6-naphthy = 2,6-naphthyridine) and {Fe(2,6-naphthy)- [Au(CN)2]2}·0.5PhNO2 (2) were synthesized and characterized. Both derivatives are made up of infinite stacks of {Fe[Ag(CN)2]2- [Ag2(CN)3]}n and {Fe[Au(CN)2]2}n layered grids connected by pillars of 2,6-naphthy ligands coordinated to the axial positions of the FeII centers of alternate layers.

{[Hg(SCN)3]2(n-L)}2-: An Efficient Secondary Building Unit for the Synthesis of 2D Iron(II) Spin-Crossover Coordination Polymers

[EN] We report an unprecedented series of two-dimensional (2D) spin-crossover (SCO) heterobimetallic coordination polymers generically formulated as {Fe-II[(He(SCN)(3))(2)](L)(x))}center dot Solv, where x = 2 for L = tvp (trans-(4,4'-vinylenedipyridine)) (1tvp), bpmh ((1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine) (1bpmh center dot nCH(3)OH; n = 0, 1), by eh ( (1E,2E)-1,2-bis (1-(pyridin-4-yl) ethyliden e) hydrazine) (Ibpeh center dot nH(2)O; n = 0, 1) and x = 2.33 for L = 0 0 bpbz (1,4-bis(pyridin-4-yl)benzene) (1bpbz center dot nH(2)O; n = 0, 2/ 3). The results confirm that self-assembly of Fell, [Hg-II(SCN)(4)](2-), and ditopic rodlike bridging ligands L containing 4-pyridyl moieties f…

Mössbauer investigation of the photoexcited spin states and crystal structure analysis of the spin-crossover dinuclear complex [{Fe(bt)(NCS)(2)}(2)bpym] (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine).

The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) e…

ChemInform Abstract: Enantioselective Friedel-Crafts Alkylation of Indoles with (E)-1-Aryl-4-benzyloxybut-2-en-1-ones Catalyzed by an (R)-3,3′-Br2BINOLate-Hafnium(IV) Complex.

A highly enantioselective Friedel–Crafts reaction of unprotected indoles with (E)-1-aryl-4-benzyloxybut-2-en-1-ones catalyzed by a new chiral [Hf{(R)-3,3′-Br2-BINOL}(OtBu)2]2 complex has been developed to functionalize the C-3 position of the indole nucleus with a side chain bearing a 1,4-difunctionalized moiety and a benzylic stereogenic center. The reaction proceeds in good to excellent yields and excellent enantioselectivities (up to 97 % ee). The usefulness of this approach was illustrated with the synthesis of a tryptophol derivative.

Hydroxy-Directed Enantioselective Hydroxyalkylation in the Carbocyclic Ring of Indoles

[EN] A Cinchona-derived squaramide catalyzes the reaction between hydroxyindoles and isatins leading to enantioenriched indoles substituted in the carbocyclic ring. The reaction proceeds efficiently with differently substituted isatins, yielding the desired products with excellent regioselectivity, good yields, and high enantiocontroi. Moreover, every position of the carbocyclic ring of the indole can be functionalized by using the appropriate starting hydroxyindole. The OH group was removed smoothly upon hydrogenolysis of the corresponding triflate.

Organocatalytic Enantioselective Synthesis of α-Hydroxyketones through a Friedel−Crafts Reaction of Naphthols and Activated Phenols with Aryl- and Alkylglyoxal Hydrates

[EN] An efficient organocatalytic asymmetric synthesis of alpha-hydroxyketones has been developed. Quinine-derived thiourea catalyzed the enantioselective Friedel Crafts alkylation of naphthols and activated phenols with aryl- and alkylglyoxal hydrates, providing the corresponding chiral alpha-hydroxyketones with high yields (up to 97%) and excellent enantioselectivities (up to 99% ee).

Enantioselective Synthesis of 2-Amino-1,1-diarylalkanes Bearing a Carbocyclic Ring Substituted Indole through Asymmetric Catalytic Reaction of Hydroxyindoles with Nitroalkenes

[EN] An asymmetric catalytic reaction of hydroxyindoles with nitroalkenes leading to the Friedel-Crafts alkylation in the carbocyclic ring of indole is presented. The method is based on the activating/directing effects of the hydroxy group situated in the carbocyclic ring of the indole providing nitroalkylated indoles functionalizated at the C-4, C-5, and C-7 positions with high yield, regio-, and enantioselectivity. The optically enriched nitroalkanes were transformed efficiently in optically enriched 2-amino-1,1-diarylalkanes bearing a carbocyclic ring substituted indole.

Aza-Henry Reaction of Isatin Ketimines with Methyl 4-Nitrobutyrate en Route to Spiro[piperidine-3,3′-oxindoles]

A new enantioselective route to spiro[piperidine-3,3′-oxindoles] from isatin ketimines is described. The aza-Henry reaction of N-Boc-isatin ketimines with methyl 4-nitrobutyrate in the presence of a Ph2BOX-CuBr2 complex provided the corresponding nitro amino esters with good diastereoselectivity and excellent enantioselectivity (up to >99% ee). The aza-Henry adducts were transformed into spiro[piperidine-3,3′-oxindoles] after reduction of the nitro group to oxime, and cleavage of the N-Boc group and lactamisation.

Polymeric Spin-Crossover Materials

Two-dimensional assembling of 4,4'-bipyridine and 4,4'-azopyridine bridged iron(II) linear coordination polymers via hydrogen bond

[EN] Novel two-dimensional polymers, [Fe(L-1)(H2O)(2)(NCX)(2)]. L-1 (L-1 =4.4'-bipyridine (bipy)) (1, 2) and [Fe(L-2)(CH3OH)(2)-(NCX)(2)]. L-2 (L-2 =4,4'-azopyridine (azpy)) (3) and X = S (1, 3), Se (2), have been synthesized and characterized by X-ray crystallography. The structures reveal the formation of tranzs-L-bridged [Fe(NCX)(2)(Y)(2)] where Y=H2O, CH3OH linear chains assembled into two-dimensional networks by hydrogen bonds between the uncoordinated ligand L and the coordinated solvent molecules.

Thermochromic Meltable Materials with Reverse Spin Transition Controlled by Chemical Design

International audience; We report a series of meltable FeII complexes, which, depending on the length of aliphatic chains, display abrupt forward low‐spin to high‐spin transition or unprecedented melting‐triggered reverse high‐spin to low‐spin transition on temperature rise. The reverse spin transition is perfectly reproducible on thermal cycling and the obtained materials are easily processable in the form of thin film owing to their soft‐matter nature. We found that the discovered approach represents a potentially generalizable new avenue to control both the location in temperature and the direction of the spin transition in meltable compounds.

Single-Crystal X-Ray Diffraction Study of Pressure and Temperature-Induced Spin Trapping in a Bistable Iron(II) Hofmann Framework.

High-pressure single-crystal X-ray diffraction has been used to trap both the low-spin (LS) and high-spin (HS) states of the iron(II) Hofmann spin crossover framework, [FeII (pdm)(H2 O)[Ag(CN)2 ]2 ⋅H2 O, under identical experimental conditions, allowing the structural changes arising from the spin-transition to be deconvoluted from previously reported thermal effects.

Synthesis, Crystal Structure, and Magnetic Properties of an Octanuclear Nickel(II) Complex with ahexahedro-Ni8 Core

Spiroterpenoids from Hypericum reflexum

Abstract Two new spiroterpenoids, hyperireflexolide A and B, were isolated from Hypericum reflexum . Their structures and stereochemistry were established by spectroscopic methods, including 13 C NMR, DEPT and HMQC, and X-ray data.

Thermo-, piezo-, photo- and chemo-switchable spin crossover iron(II)-metallocyanate based coordination polymers

Abstract The design of coordination polymers (CPs) with switch and memory functions is an important subject of current interest in the search for new advanced materials with potential applications. Implementation of CPs with electronically labile iron(II) building blocks able to undergo cooperative spin crossover (SCO) behavior is a singular approach to this end. This review provides an up to date survey of a new generation of iron(II)-metallocyanate based spin crossover coordination polymers (SCO-CPs) developed during the last decade. These new solids feature structural diversity, supramolecular isomerism, interpenetrating frameworks, structure flexibility, reversible solid-state chemical …

Thermal- and photoinduced spin-state switching in an unprecedented three-dimensional bimetallic coordination polymer.

The compound {Fe(pmd)[Ag(CN)2][Ag2(CN)3]} (pmd=pyrimidine) was synthesized and characterized. Magnetic, calorimetric and single crystal visible spectroscopic studies demonstrate the occurrence of a two-step high-spin (HS) right arrow over left arrow low-spin (LS) transition. The critical temperatures are T(c1)=185 and T(c2)=148 K. Each step involves approximately 50 % of the iron centers, with the low-temperature step showing a hysteresis of 2.5 K. The enthalpy and entropy variations associated with the two steps are DeltaH(1)=3.6+/-0.4 kJ mol(-1) and DeltaS(1)=19.5+/-3 J K(-1) mol(-1); DeltaH(2)=4.8+/-0.4 kJ mol(-1) and DeltaS(2)=33.5+/-3 J K(-1) mol(-1). Photomagnetic and visible spectros…

A Square-Planar Dinickel(II) Complex with a Noninnocent Dinucleating Oxamate Ligand: Evidence for a Ligand Radical Species

[EN] The new bimetallic nickel(II) compound (PPh4)4[Ni2(2)]·6H2O (3), where H8[2] stands for N,N',N'',N'''-1,2,4,5-benzene-tetrayltetrakis(oxamic acid), has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. The structure of 3 consists of [Ni2(n4:n4-2)]4- anions, tetraphenylphosphonium cations, and water molecules. Facile one-electron oxidation of the square-planar diamagnetic dinickel(II) complex [Ni2(n4:n4-2)]4- generates the metallo-radical species [Ni2(n4:n4-2·+)]3- with characteristic intra-ligand ¿cation radical transitions in the visible region (475-550 nm) as well as a typical quasi-isotropic EPR signal at g ¿ 2.0.

ChemInform Abstract: Enantioselective Addition of Nitromethane to 2-Acylpyridine N-Oxides. Expanding the Generation of Quaternary Stereocenters with the Henry Reaction.

The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or α-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.

A Hydrogen-Bonded Supramolecular meso-Helix

[EN] A new one-dimensional hydrogen-bonded polymer with a unique meso-helical structure has been prepared from the spontaneous self-assembly in the solid-state of meta-substituted phenylene dioxamic acid diethyl ester monomers. The helical nature of this molecule and its self-complementary character, through intermolecular hydrogen bonding between oxamic acid ester functions, are the two main factors responsible for the crystalline aggregation process, as confirmed by both experimental X-ray crystallographic data and theoretical ab initio calculations.

Spin Crossover and Paramagnetic Behaviour in Two-Dimensional Iron(II) Coordination Polymers with Stilbazole Push–Pull Ligands

The suitability of the stilbazole push–pull ligands, 4′-dimethylaminostilbazole (DMAS) and 4′-diethylaminostilbazole (DEAS), for the construction of bimetallic FeII–AgI/AuI cyanide-based coordination polymers that exhibit spin crossover properties is investigated. The structural and physical characterization of four novel two-dimensional FeII polymers formulated as {Fe(DMAS)2[Ag(DMAS)(CN)2]2} (1) and {Fe(L)2[M(CN)2]2} (L = DMAS, M = Au (2); DEAS, Ag (3); DEAS, Au (4)) is reported. Polymers 1 and 4 are paramagnetic over the whole range of temperatures studied (5–300 K), whereas 2 and 3 exhibit spin crossover properties.

Organocatalytic enantioselective aza-Friedel–Crafts reaction of 2-naphthols with benzoxathiazine 2,2-dioxides

An organocatalytic enantioselective aza-Friedel–Crafts addition of 2-naphthols to benzoxathiazine 2,2-dioxides is described using a quinine-derived bifunctional catalyst. The method allows the use of a wide range of aromatic compounds as nucleophiles, including 1-naphthol and sesamol, and benzoxathiazines 2,2-dioxides, expanding the existing state of the art enantioselective synthesis of aminomethylnaphthol derivatives.

Inside Cover: Bidirectional Chemo-Switching of Spin State in a Microporous Framework (Angew. Chem. Int. Ed. 26/2009)

Bidirectional chemo-switching of magnetism occurs in a microporous coordination polymer containing spin-crossover subunits, as described by M. Ohba, J. A. Real, S. Kitagawa, and co-workers in their Communication on page 4767 ff. In situ magnetic measurements reveal that most guest molecules transform the framework spin state from diamagnetic low spin (red) to paramagnetic high spin (yellow), whereas the guest CS2 stabilizes the low-spin state. These induced spin states are retained as a memory effect after the release of the guest.

A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture

High-valent bis(oxo)-bridged dinuclear manganese oxamates: Synthesis, crystal structures, magnetic properties, and electronic structure calculations of bis(μ-oxo)dimanganese(IV) complexes with a binucleating o-phenylenedioxamate ligand

[EN] Two novel bis(oxo)-bridged dinuclear manganese(IV) complexes with the binucleating ligand o-phenylenebis(oxamate) (opba), formulated as (Me4N)(4)[Mn2O2(opba)(2)] (1a) and (Me4N)(2)(Ph4P)(2)[Mn2O2(opba)(2)] (.) 8H(2)O (1b), have been synthesized and characterized structurally and magnetically. Like the parent complex (Ph4P)(4)[Mn2O2(opba)(2)] (.) 4H(2)O (1c), they possess unique Mn-2(mu-O)(2) bridging cores with two additional o-phenylenediamidate bridges which lead to exceptionally short Mn-Mn distances (2.63-2.67 angstrom) and fairly bent Mn-O-Mn angles (93.8-95.5 degrees). Complexes 1a-c show a moderate to strong antiferromagnetic coupling between the two high-spin Mn-IV ions through…

A novel dimer of oxo-di(acetato)-bridged manganese(III) dimers complex of potential biological significance

[EN] Assembly of the tetranuclear oxomanganese(III) acetato cluster [Mn4O2(O2CMe)(7)(phen)(2)](BF4) from the dinuclear oxo-di(acetato)bridged manganese(III) species [Mn2O(O2CMe)(2)(H2O)(2)(phen)(2)](BF4)(2) . 3H(2)O in aqueous/acetic acid MeOH solution occurs via the new 'dimer of dimers' Mn-III complex [Mn2O(O2CMe)(3)(H2O)(phen)(2)](BF4) . MeOH possesing an unprecedent [Mn-4(mu-O)(2)(mu-O2Me)(4) (mu-(OH2O2CMe)-O-...)(2)] core.

Efficient Synthesis of 5-Chalcogenyl-1,3-oxazin-2-ones by Chalcogen-Mediated Yne-Carbamate Cyclisation: An Experimental and Theoretical Study

A very efficient synthesis of 5-chalcogenyl-1,3-oxazin-2-ones has been accomplished by the chalcogen-mediated yne–carbamate cyclisation of chiral, non-racemic N-Cbz-protected propargylic amines using PhXY (X = Se, S, Te; Y = Br or Cl) as electrophile sources. The reactions gave good-to-excellent yields for a wide range of substrates. In all cases the reaction was totally regioselective, occurring by a 6-endo-dig process regardless of the nature of the reagent and of the substituents in the starting material. This methodology permits the formation of the 1,3-oxazin-2-one moiety as well as the simultaneous installation of a chalcogen functionality onto the heterocyclic ring. The experimental …

Competing Phases Involving Spin-State and Ligand Structural Orderings in a Multistable Two-Dimensional Spin Crossover Coordination Polymer

[EN] Competition between spin-crossover and structural ligand ordering is identified as responsible for multistability and generation of six different phases in a rigid two-dimensional coordination polymer formulated {Fe-II[Hg-II(SCN)(3)](2) mu-(4,4'-bipy)(2)}(n) (1) (4,4'-bipy = 4,4'-bipyridine). The structure of 1 consists of infinite linear [Fe(mu-4,4'-bipy)](n)(2n+) chains linked by in situ formed {[Hg-II(SCN)(3)](2)(mu-4,4'-bipy)}(2n-) anionic dimers. The thermal dependence of the high-spin fraction, his, features four magnetic phases defined by steps following the sequence gamma(HS) = 1 (phase 1) gamma(HS) = 1/2 (phase 2) gamma(HS) approximate to 1/3 (phase 3) gamma(HS) = 0 (phase 4) …

Manganese(III)-mediated oxidative carbon-carbon bond cleavage of the 1,10-phenanthroline-5,6-dione ligand

[EN] A new manganese(III)-1,10-phenanthroline-5,6-dione (phendione) complex possessing a putative Mn-2(mu-O) (mu-O2CMe)(2) core has been found to undergo a Ligand-based oxidative cleavage of the C(5)-C(6) bond in weak acid aqueous MeOH under aerobic conditions at room temperature to yield 2,2'-bipyridyl-3,3'-dicarboxylate with co-reduction to the corresponding Mn-II-phendione species.

CCDC 2018380: Experimental Crystal Structure Determination

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CCDC 1972870: Experimental Crystal Structure Determination

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CCDC 1544708: Experimental Crystal Structure Determination

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CCDC 1007129: Experimental Crystal Structure Determination

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CCDC 1042612: Experimental Crystal Structure Determination

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CCDC 971025: Experimental Crystal Structure Determination

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CCDC 1965274: Experimental Crystal Structure Determination

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CCDC 1521585: Experimental Crystal Structure Determination

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CCDC 1521589: Experimental Crystal Structure Determination

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CCDC 2018391: Experimental Crystal Structure Determination

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CCDC 1550080: Experimental Crystal Structure Determination

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CCDC 1464259: Experimental Crystal Structure Determination

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CCDC 1013100: Experimental Crystal Structure Determination

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CCDC 1417554: Experimental Crystal Structure Determination

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CCDC 684617: Experimental Crystal Structure Determination

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CCDC 1521590: Experimental Crystal Structure Determination

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CCDC 1847752: Experimental Crystal Structure Determination

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CCDC 1050042: Experimental Crystal Structure Determination

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CCDC 1953086: Experimental Crystal Structure Determination

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CCDC 2016312: Experimental Crystal Structure Determination

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CCDC 1852557: Experimental Crystal Structure Determination

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CCDC 1572177: Experimental Crystal Structure Determination

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CCDC 1572180: Experimental Crystal Structure Determination

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CCDC 1879899: Experimental Crystal Structure Determination

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CCDC 1879896: Experimental Crystal Structure Determination

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CCDC 971023: Experimental Crystal Structure Determination

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CCDC 1042617: Experimental Crystal Structure Determination

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CCDC 1444032: Experimental Crystal Structure Determination

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CCDC 1521583: Experimental Crystal Structure Determination

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CCDC 1572183: Experimental Crystal Structure Determination

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CCDC 1572184: Experimental Crystal Structure Determination

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CCDC 1042613: Experimental Crystal Structure Determination

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CCDC 1818227: Experimental Crystal Structure Determination

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CCDC 1897989: Experimental Crystal Structure Determination

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CCDC 1910592: Experimental Crystal Structure Determination

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CCDC 1050041: Experimental Crystal Structure Determination

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CCDC 2018392: Experimental Crystal Structure Determination

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CCDC 1565402: Experimental Crystal Structure Determination

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CCDC 1020145: Experimental Crystal Structure Determination

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CCDC 1050040: Experimental Crystal Structure Determination

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CCDC 1020141: Experimental Crystal Structure Determination

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CCDC 1879901: Experimental Crystal Structure Determination

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CCDC 1557026: Experimental Crystal Structure Determination

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CCDC 1572181: Experimental Crystal Structure Determination

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CCDC 1535017: Experimental Crystal Structure Determination

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CCDC 1989161: Experimental Crystal Structure Determination

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CCDC 1457784: Experimental Crystal Structure Determination

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CCDC 941482: Experimental Crystal Structure Determination

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CCDC 1944351: Experimental Crystal Structure Determination

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CCDC 1418191: Experimental Crystal Structure Determination

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CCDC 1953087: Experimental Crystal Structure Determination

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CCDC 1020147: Experimental Crystal Structure Determination

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CCDC 1989160: Experimental Crystal Structure Determination

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CCDC 684616: Experimental Crystal Structure Determination

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CCDC 1989157: Experimental Crystal Structure Determination

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CCDC 1889981: Experimental Crystal Structure Determination

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CCDC 1847351: Experimental Crystal Structure Determination

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CCDC 1910990: Experimental Crystal Structure Determination

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CCDC 1961393: Experimental Crystal Structure Determination

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CCDC 1418192: Experimental Crystal Structure Determination

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CCDC 1879898: Experimental Crystal Structure Determination

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CCDC 904082: Experimental Crystal Structure Determination

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CCDC 904083: Experimental Crystal Structure Determination

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CCDC 2010363: Experimental Crystal Structure Determination

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CCDC 1994888: Experimental Crystal Structure Determination

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CCDC 1457782: Experimental Crystal Structure Determination

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CCDC 2209231: Experimental Crystal Structure Determination

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CCDC 2209228: Experimental Crystal Structure Determination

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CCDC 1402446: Experimental Crystal Structure Determination

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CCDC 1050034: Experimental Crystal Structure Determination

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CCDC 1048103: Experimental Crystal Structure Determination

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CCDC 1020143: Experimental Crystal Structure Determination

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CCDC 1060123: Experimental Crystal Structure Determination

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CCDC 1455020: Experimental Crystal Structure Determination

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CCDC 684618: Experimental Crystal Structure Determination

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CCDC 1007130: Experimental Crystal Structure Determination

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CCDC 1852556: Experimental Crystal Structure Determination

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CCDC 1455021: Experimental Crystal Structure Determination

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CCDC 1457780: Experimental Crystal Structure Determination

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CCDC 1007126: Experimental Crystal Structure Determination

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CCDC 1418190: Experimental Crystal Structure Determination

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CCDC 2209227: Experimental Crystal Structure Determination

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CCDC 1844052: Experimental Crystal Structure Determination

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CCDC 1910594: Experimental Crystal Structure Determination

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CCDC 2018389: Experimental Crystal Structure Determination

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CCDC 1521587: Experimental Crystal Structure Determination

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CCDC 2122953: Experimental Crystal Structure Determination

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CCDC 1847352: Experimental Crystal Structure Determination

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CCDC 1572182: Experimental Crystal Structure Determination

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CCDC 975036: Experimental Crystal Structure Determination

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CCDC 1505242: Experimental Crystal Structure Determination

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CCDC 1989159: Experimental Crystal Structure Determination

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CCDC 1401764: Experimental Crystal Structure Determination

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CCDC 975041: Experimental Crystal Structure Determination

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CCDC 1585097: Experimental Crystal Structure Determination

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CCDC 1844051: Experimental Crystal Structure Determination

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CCDC 2018381: Experimental Crystal Structure Determination

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CCDC 1922649: Experimental Crystal Structure Determination

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CCDC 1910992: Experimental Crystal Structure Determination

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CCDC 1503457: Experimental Crystal Structure Determination

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CCDC 684615: Experimental Crystal Structure Determination

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CCDC 1910593: Experimental Crystal Structure Determination

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CCDC 1020146: Experimental Crystal Structure Determination

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CCDC 1821100: Experimental Crystal Structure Determination

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CCDC 1970081: Experimental Crystal Structure Determination

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CCDC 1846586: Experimental Crystal Structure Determination

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CCDC 1852560: Experimental Crystal Structure Determination

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CCDC 2010365: Experimental Crystal Structure Determination

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CCDC 1457779: Experimental Crystal Structure Determination

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CCDC 1897988: Experimental Crystal Structure Determination

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CCDC 1879900: Experimental Crystal Structure Determination

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CCDC 1050032: Experimental Crystal Structure Determination

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CCDC 1550075: Experimental Crystal Structure Determination

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CCDC 971022: Experimental Crystal Structure Determination

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CCDC 941483: Experimental Crystal Structure Determination

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CCDC 1402447: Experimental Crystal Structure Determination

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CCDC 684614: Experimental Crystal Structure Determination

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CCDC 1405184: Experimental Crystal Structure Determination

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CCDC 1565404: Experimental Crystal Structure Determination

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CCDC 971024: Experimental Crystal Structure Determination

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CCDC 1965275: Experimental Crystal Structure Determination

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CCDC 1439710: Experimental Crystal Structure Determination

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CCDC 1415301: Experimental Crystal Structure Determination

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CCDC 975039: Experimental Crystal Structure Determination

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CCDC 1585098: Experimental Crystal Structure Determination

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CCDC 1417556: Experimental Crystal Structure Determination

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CCDC 2018390: Experimental Crystal Structure Determination

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CCDC 1550084: Experimental Crystal Structure Determination

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CCDC 1897990: Experimental Crystal Structure Determination

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CCDC 2018379: Experimental Crystal Structure Determination

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CCDC 1821099: Experimental Crystal Structure Determination

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CCDC 1020142: Experimental Crystal Structure Determination

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CCDC 1521586: Experimental Crystal Structure Determination

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CCDC 1890014: Experimental Crystal Structure Determination

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CCDC 1965272: Experimental Crystal Structure Determination

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CCDC 1894402: Experimental Crystal Structure Determination

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CCDC 2010361: Experimental Crystal Structure Determination

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CCDC 1544707: Experimental Crystal Structure Determination

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CCDC 1050039: Experimental Crystal Structure Determination

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CCDC 1972869: Experimental Crystal Structure Determination

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CCDC 1852559: Experimental Crystal Structure Determination

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CCDC 1965273: Experimental Crystal Structure Determination

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CCDC 1042615: Experimental Crystal Structure Determination

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CCDC 1892385: Experimental Crystal Structure Determination

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CCDC 1020140: Experimental Crystal Structure Determination

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CCDC 1565403: Experimental Crystal Structure Determination

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CCDC 1042614: Experimental Crystal Structure Determination

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CCDC 2018384: Experimental Crystal Structure Determination

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CCDC 1442206: Experimental Crystal Structure Determination

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CCDC 916051: Experimental Crystal Structure Determination

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CCDC 1992564: Experimental Crystal Structure Determination

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CCDC 2018386: Experimental Crystal Structure Determination

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CCDC 1585096: Experimental Crystal Structure Determination

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CCDC 1439713: Experimental Crystal Structure Determination

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CCDC 1050043: Experimental Crystal Structure Determination

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CCDC 2018388: Experimental Crystal Structure Determination

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CCDC 2010360: Experimental Crystal Structure Determination

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CCDC 1875758: Experimental Crystal Structure Determination

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CCDC 1521584: Experimental Crystal Structure Determination

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CCDC 1417555: Experimental Crystal Structure Determination

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CCDC 861026: Experimental Crystal Structure Determination

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CCDC 1050036: Experimental Crystal Structure Determination

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CCDC 1585094: Experimental Crystal Structure Determination

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CCDC 1050033: Experimental Crystal Structure Determination

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CCDC 2209230: Experimental Crystal Structure Determination

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CCDC 987530: Experimental Crystal Structure Determination

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CCDC 1910591: Experimental Crystal Structure Determination

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CCDC 1046444: Experimental Crystal Structure Determination

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CCDC 1585095: Experimental Crystal Structure Determination

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CCDC 1007125: Experimental Crystal Structure Determination

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CCDC 1970080: Experimental Crystal Structure Determination

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CCDC 2209233: Experimental Crystal Structure Determination

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CCDC 2024661: Experimental Crystal Structure Determination

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CCDC 1965271: Experimental Crystal Structure Determination

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CCDC 1550083: Experimental Crystal Structure Determination

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CCDC 1852562: Experimental Crystal Structure Determination

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CCDC 1989162: Experimental Crystal Structure Determination

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CCDC 987531: Experimental Crystal Structure Determination

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CCDC 2010362: Experimental Crystal Structure Determination

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CCDC 1894403: Experimental Crystal Structure Determination

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CCDC 975037: Experimental Crystal Structure Determination

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CCDC 1899761: Experimental Crystal Structure Determination

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CCDC 2010366: Experimental Crystal Structure Determination

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CCDC 1581116: Experimental Crystal Structure Determination

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CCDC 1965270: Experimental Crystal Structure Determination

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CCDC 1007128: Experimental Crystal Structure Determination

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CCDC 1050038: Experimental Crystal Structure Determination

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CCDC 1535016: Experimental Crystal Structure Determination

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CCDC 1550074: Experimental Crystal Structure Determination

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CCDC 1862017: Experimental Crystal Structure Determination

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CCDC 904080: Experimental Crystal Structure Determination

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CCDC 1572179: Experimental Crystal Structure Determination

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CCDC 1530500: Experimental Crystal Structure Determination

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CCDC 1572178: Experimental Crystal Structure Determination

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CCDC 1439487: Experimental Crystal Structure Determination

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CCDC 1020148: Experimental Crystal Structure Determination

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CCDC 1020149: Experimental Crystal Structure Determination

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CCDC 1989158: Experimental Crystal Structure Determination

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CCDC 1042616: Experimental Crystal Structure Determination

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CCDC 1007127: Experimental Crystal Structure Determination

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CCDC 1550078: Experimental Crystal Structure Determination

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CCDC 2018382: Experimental Crystal Structure Determination

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CCDC 1020144: Experimental Crystal Structure Determination

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CCDC 2018383: Experimental Crystal Structure Determination

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CCDC 1970083: Experimental Crystal Structure Determination

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