Low-temperature Ti-containing 3:2 and 2:1 mullite nanocrystals from single-phase gels

Abstract TiO 2 -containig single-phase gels with (Al 2 O 3  + TiO 2 )/(SiO 2 ) molar ratios 3/2 and 2/1 were prepared by gelling mixtures of aluminium nitrate, tetraethylorthosilicate and titanium isopropoxide. Gels were fast heated at several temperatures up to 1100 °C. Dried and heated gels were characterized by differential thermal analysis (DTA), magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray powder diffraction (XRD), and scanning and transmission electron microscopies (SEM and TEM). Coupled DTA and XRD results of gels fast heated at 900 °C showed the crystallisation of two mullites as well as a small amount of alumina-silica spinel. 27 Al NMR spectra showed the format…

Acid-Promoted Rearrangement of the Metalated Thienyl Rings in Dirhodium(II) Complexes with Thienyl Phosphines as Ligands

Several mono- and bis-cyclometalated compounds have been prepared and characterized from the thermal reaction of dirhodium(II) tetraacetate and tris(2-thienyl)phosphine, P(2-C4H3S)3 (1), in toluene/acetic acid mixtures. In refluxing acetic acid, the mono-cyclometalated compound Rh2(O2CCH3)3[(2-C4H2S)P(2-C4H3S)2] (CH3CO2H)2 (2A) isomerizes to Rh2(O2CCH3)3[(3-C4H2S)P(2-C4H3S)2](CH3CO2H)2 (2B), which results from the selective rearrangement of the metalated ring from a 2-thienyl to a 3-thienyl structure. In the same conditions, the bis-cyclometalated compounds of formula Rh2(O2CCH3)2[(2-C4H2S)P(2-C4H3S)2]2(CH3CO2H)2 and with head-to-tail (3AA) or head-to-head (4AA) configuration of the phosphi…

Synthesis and X-ray Crystallographic Characterization of (μ-(Diphenylphosphino)phenyl-C2,P)palladium Bromide. A Novel Tetranuclear Metalated Compound

The synthesis and crystal structure of a tetranuclear palladium cluster, [Pd(PC)Br]4 (PC) = [P(C6H4)Ph2]-), is described. Cleavage of this cluster with phosphines yields the mononuclear species Pd(PC)Br(P) in the form of cis and trans isomers. An equilibrium between mono- and tetranuclear species is observed for P = PCBr.

Triazolopyridopyrimidines: an emerging family of effective DNA photocleavers. DNA binding. Antileishmanial activity.

Triazolopyridopyrimidines 3-phenyl-6,8-di(2-pyridyl)-[1,2,3]triazolo[5',1':6,1]pyrido[2,3-d]pyrimidine (1a), 6,8-di(pyridin-2-yl)-[1,2,3]triazolo[1',5':1,6]pyrido[2,3-d]pyrimidine (1b) and 3-methyl-6,8-di(2-pyridyl)-[1,2,3]triazolo[5',1':6,1]pyrido[2,3-d]pyrimidine (1c) were prepared and their electrochemical and luminescence properties were studied in depth. The DNA binding ability of this series of compounds has been investigated by means of UV-vis absorption and fluorescence titrations, steady-state emission quenching with ferrocyanide as well as viscosity measurements. Results have shown that triazolopyridopyrimidine 1a interacts strongly at DNA grooves. This compound also displays pref…

Enantio- and Diastereocontrol in Intermolecular Cyclopropanation Reaction of Styrene Catalyzed by Dirhodium(II) Complexes with Bulky ortho-Metalated Aryl Phosphines:  Catalysis in Water as Solvent. Study of a (+)-Nonlinear Effect

Enantiomerically pure dirhodium(II) complexes with ortho-metalated para-substituted aryl phosphines have been shown to lead to an enantio- and diastereoselective cyclopropanation of styrene with ethyl diazoacetate. Enantioselectivities up to 91% and diastereoselectivities up to 90% are observed for ethyl cis-2-phenylcyclopropanecarboxylate. High enantio- and diastereoselectivities are observed for the synthesis of ethyl cis-2-phenylcyclopropanecarboxylate using water as solvent. Additionally, a (+)-nonlinear effect, (+)-NLE, has been observed and studied in the asymmetric catalytic reaction developed in n-pentane.

Dirhodium(II) compounds with bridging thienylphosphines: studies on reversible P,C/P,S coordination.

Monocyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(CH(3)CO(2)H)(2)(O(2)CCH(3))(3)] (1 a) and bis-cyclometalated compound [Rh(2){(C(8)H(4)S)P(C(8)H(5)S)(2)}(2)(CH(3)CO(2)H)(2)(O(2)CCH(3))(2)] (2 a) have been isolated from the reaction of dirhodium tetraacetate and tris(2-benzo[b]thienyl)phosphine (2 BTP) using low acidic solutions. By contrast, in pure acetic acid the reaction of Rh(2)(O(2)CCH(3))(4) with 2 BTP and tris(2-thienyl)phosphine (2 TP), followed by replacement of the axial acetate ligands by chlorides, led to [Rh(2){(2-C(8)H(5)S)P(2-C(8)H(5)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (3 b) and [Rh(2){(2-C(4)H(3)S)P(C(4)H(3)S)(2)}(2)Cl(2)(O(2)CCH(3))(2)] (5 b), respectively. These n…

Electrochemical study of dinuclear ruthenium(II)—arene compounds: Electrogeneration of Ru(II)—Ru(I) species

Abstract The preparation and characterization of Ru(II)—arene compounds [{RuCl2(p-cym)}2(μ-L-L)] where p-cym = p-MeC6H4CHMe2; and L-L = diphenylphosphinomethane (I), 1,1′-bisdiphenylphosphinoferrocene (II), pyrazine (III) and 4,4′-bipyridine (IV), are described. Electrochemical data for these compounds obtained by cyclic voltammetry and coulometry are reported. The electrochemical reduction of compounds I or II yields ruthenium(O) species. However, compounds III or IV containing ligands with delocalized Π orbitals undergo one-electron reduction. The ESR signal detected during the electrolysis of compounds III or IV is consistent with one delocalized electron through the whole dinuclear unit.

Orthometallation reaction in dirhodium(II) compounds. Selective formation of doubly-metallated compounds with head-to-head structure

Abstract The reaction of the mono-metallated compound Rh 2 (O 2 CCH 3 ) 3 [(C 6 H 4 )P(CH 3 ) (C 6 H 5 )]·2(HO 2 CCH 3 ) with PPh 3 (1:1 molar ratio) has been studied by 31 P NMR spectroscopy. The reaction yields the doubly-metallated compound Rh 2 (O 2 CCH 3 ) 2 [(C 6 H 4 ) P(CH 3 )(C 6 H 5 )]p(C 6 H 4 )P(C 6 H 5 ) 2 ]·2(HO 2 CCH 3 ) with a head-to-head (H-H) configuration. An intermediate reaction compound, not previously observed, has been spectroscopically detected in solution. Analogous intermediate compounds have been detected using P( p -CH 3 C 6 H 4 ) 3 and P( p -ClC 6 H 4 ) 3 instead of triphenylphosphine.

ChemInform Abstract: Synthesis and X-Ray Structure of Metalated Rhodium(II) Catalysts with a Chiral Phospholane.

The reaction of Rh2(O2CR)4 (R = CH3, CF3) with the chiral phosphane (2S,5S)-2,5-dimethyl-1-phenylphospholane (PC*H), results in the formation of two diastereoisomers of Rh2(O2CCR)2(PC*)2, with (P) and (M) configuration. These can easily be isolated by chromatographic methods to obtain enantiomerically pure RhII compounds. Preliminary catalytic studies have shown that they induce moderate asymmetry in the cyclization of 5-aryl-1-diazo-2-pentanones and 1-diazo-5-hexen-2-one. X-ray analysis of the (M) diastereoisomer with formula Rh2(O2CCCH3)2(PC*)2 is reported. The crystallographic parameters are as follows: space group P21212 (orthorhombic) with a = 12.1347(11) A, b = 14.5870(13) A, c = 9.81…

Crystal structures and spectroscopic properties of copper(II)–bis(2-pyridylcarbonyl)amide–chlorobenzoate complexes

The reaction of 2,4,6-tris(pyridyl)-1,3,5-triazine (ptz) and copper(II) salts in DMF–water (4:1) resulted in the hydrolysis of ptz, giving rise to the bis(2-pyridylcarbonyl)amide anion ( ptO 2 - ) and affording the complexes [Cu(ptO 2 )(2-Clbenz)(H 2 O)] ( 1 ), [Cu(ptO 2 )(3-Clbenz)] ( 2 ), and [Cu(ptO 2 )(4-Clbenz)(DMF)] ( 3 ). This report includes the chemical and spectroscopic characterization of all these compounds along with the crystal structures of the Cu(II) complexes thus formed. The coordination spheres of Cu(II) in 1 and 3 are best described as distorted square based pyramidal, while for 2 the coordination sphere is distorted square planar.

Synthesis, characterization and kinetics of the metallation of the intermediate compound to produce compound · (H2O) from Rh(II) tetraacetate

Abstract Photochemical irradiation of mixtures of [Rh2(μ-O2CCH3)4]·(HOCH3)2 and P(2-(CH3O)C6H4)Ph2 (POMe) in CH2Cl2 solution (1:1 molar ratio) yields quantitatively compound [ Rh 2 (μ- O 2 CCH 3 ) 3 ( O 2 CCH 3 )(η 2 - P (2-( CH 3 O ) C 6 H 4 ) Ph 2 ]·( H 2 O ) (1) containing a POMe acting as a chelating equatorial ( P ) axial ( O ) donor ligand. This compound undergoes intramolecular CH activation reaction at one of the phenyl rings in CHCl3 or CH3COOH/toluene solution at room temperature to form the monometallated compound [ Rh 2 (μ- O 2 CCH 3 ) 3 (μ-( C C 3 H 4 ) P (2-( CH 3 O C 6 H 4 ) Ph )]· ( H 2 O ) ( 2 ). The kinetics of the 1 → bd2 reaction have been studied in acid media (CH3CO…

Immobilized Chiral ortho-Metalated Dirhodium(II) Compounds as Catalysts in the Asymmetric Cyclopropanation of Styrene with Ethyl Diazoacetate

Immobilization of ortho-metalated dirhodium(II) compounds has been achieved by a carboxylate interchange reaction between (M)-Rh2(l-protos)2[(p-XC6H3)P(p-XC6H4)2]2 diastereoisomers and carboxyethylpolystyrene polymer (PS-C6H4(CH2)2CO2H). The immobilized chiral catalysts have been tested in the standard reaction of asymmetric cyclopropanation of styrene with ethyl diazoacetate, giving higher yields than homogeneous chiral trifluoroacetate derivatives, but their diastereo- and enantioselectivities were lower. Some of the immobilized catalysts have proved to be very robust. The catalytic behavior of (M)-Rh2(O2C(CH2)2C6H5)2[(p-XC6H3)P(p-XC6H5)2]2 compounds has been studied as a model for the im…

Dinuclear Palladium(II) and -(III) Compounds with O,O-Chelating Ligands. Room-Temperature Direct 2-Phenylation of 1-Methylindole

New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[O–O]2Cl2, O–O being chelating phenolates C6H4OC(O)R (R = CH3, 3a; R = C2H5, 3b; R = OPh, 3c) or acetylacetonates RC(O)CHC(O)R (R = CH3, 4a; R = CF3, 4b; R = C(CH3)3, 4c), have been obtained by oxidation with PhICl2 of the corresponding palladium(II) compounds. The stability of the new compounds has been studied by 31P NMR spectroscopy from 200 to 298 K. DFT calculations of the stability of the complexes have also been performed. In agreement with these calculations, only compound Pd2[(C6H4)PPh2]2[(CF3C(O)CHC(O)CF3]2Cl2, 6b, showed the highest thermal stability. 6b was characterized by X-ray diffraction methods, prese…

Photo-assisted formation of a chelating diphos ligand from PPh3 and a cyclometallated [P(C6H4)(C6H5)2]− ligand. Crystal structure of Pd{η2-o-[P(C6H5)2]2(C6H4)}Br2

Abstract The cyclometallated palladium compound, Pd[η2-(C6H4)P(C6H5)2]Br[P(C6H5)3] (1), in the solid state by action of light, evolves to give Pd{η2-o-[P(C6H5)2]2(C6H4)}Br2 (2). This compound contains the diphosphine, o-[P(C6H5)2]2(C6H4), as chelated ligand that is formed by a couple reaction of the metallated ligand η2-[(C6H4)P(C6H5)2]− and the coordinated arylphosphine. A study by NMR spectroscopy confirms that the o-phenylene bridge in the diphosphine ligand in 2 comes from the metallated phosphine ligand in 1.

Analysis of the main structural trends for biscyclometalated dinuclear rhodium compounds of general formula Rh2(O2CR)2(PC)2·2H2O

Abstract A new series of biscyclometalated dinuclear rhodium (II) compounds with the general formula Rh2(O2CR)2(PC)2 · 2H2O, being PC = (C6H4)P(C6H5)2, R = CH3 (1 · 2H2O), PC = [(p-CH3 OC6H3)P(p-CH3 OC6H4)2], R = CF3 (2 · 2H2O), PC = (C6H4)P[CH(CH3)2]2, R = CH3 (3 · 2H2O) and PC = (C6H4)P(C6H5)2, R = C6F5 (4 · 2H2O) has been obtained. The crystal structures for these compounds have been determined by X-ray diffraction and the main structural trends, bond lengths, bond angles and torsion angles have been analyzed, and have also been compared with the structural parameters for different analogous complexes described previously in the literature.

Electrochemical study on a tricyclic 1,1,1-tricar-bonyl-2,3-1 diazaferrole derivative. II. Activation of carbon monoxide replacement by electron transfer processes

Etudes, par voltammetrie cyclique, de la reduction electrochimique du complexe de diazaferratricyclodecene, en presence de P(OMe) 3

Triazenides as Suitable Ligands in the Synthesis of Palladium Compounds in Three Different Oxidation States: I, II, and III

New orthometalated dinuclear triazenide palladium(II) compounds of the general formula Pd2[(C6H4)PPh2]2[R–N–N–N–R]2 (R = C6H5, 3a; o-BrC6H4, o-3b; o-MeOC6H4, o-3c; o-MeC6H4, o-3d ; p-BrC6H4, p-3b; p-MeOC6H4, p-3c; p-MeC6H4, p-3d) have been synthesized and structurally characterized. The characteristics of these compounds were compared with the isoelectronic formamidinate derivatives. These triazenide compounds have been suitable starting products in the synthesis of new not so common dinuclear palladium(I) compounds and new unusual palladium(III) ones. In the presence of an excess of the triazenide ligand, compounds o-3b and o-3c underwent a reduction process giving dinuclear palladium(I) c…

Synthesis and reactivity of the novel hydride derivative RhHCl(TIMP3) (HTIMP3 = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane)

The reaction of HTIMP(3) (HTIMP(3) = tris[1-(diphenylphosphino)-3-methyl-1H-indol-2-yl]methane) with [RhCl(COD)](2) and Rh(acac)(CO)(2) produces RhHCl(TIMP(3)) (1H) and Rh(TIMP(3))(CO) (2), respectively, both exhibiting tetradentate kappaC,kappa(3)P-coordination of the TIMP(3) moiety. The reaction of RhHCl(TIMP(3)) with nucleophiles (L) in the presence of AgBF(4) or AgPF(6) produces different compounds depending on the nature of L. Indeed, cationic Lewis adducts of formula [RhH(L)(TIMP(3))](+) ((2H+)-(5H+)) are obtained when L is CO, CNCH(2)Ph, pyridine or CH(2)CHCN. On the other hand, when the incoming nucleophile is CH(3)COOH the hydride-free complex [Rh(CH(3)COO)(TIMP(3))](+) ((6+)) is o…

Tandem β-Boration/Arylation of α,β-Unsaturated Carbonyl Compounds by Using a Single Palladium Complex To Catalyse Both Steps

Diphenyl(3-methyl-2-indolyl)phosphine (C(9)H(8)NPPh(2), 1) gives stable dimeric palladium(II) complexes that contain the phosphine in P,N-bridging coordination mode. On treating 1 with [Pd(O(2)CCH(3))(2)], the new complexes [Pd(mu-C(9)H(7)NPPh(2))(NCCH(3))](2) (2) or [Pd(mu-C(9)H(7)NPPh(2))(mu-O(2)CCH(3))](2) (3) were isolated, depending on the solvent used, acetonitrile or toluene, respectively. Further reaction of 3 with the ammonium salt of 1 led to the substitution of one carboxylate ligand to afford [Pd(mu-C(9)H(7)NPPh(2))(3)(mu-O(2)CCH(3))] (4), in which the bimetallic unit is bonded by three C(9)H(7)NPPh(2)(-) moieties and one carboxylate group. Using this methodology, [Pd(2)(mu-C(6)…

Ligand Effects on the Chemoselectivity of Ortho-Metalated Rhodium(II) Catalyzed α-Diazo Ketone Transformations

Rh2(OOCR)2(PC)2 complexes (PC = orthometalated phosphines, OOCR = carboxylates) with very polarizable ligands, such as aromatic rings directly joined to the rhodium atoms, control chemoselectivity in competitive metal carbene transformations of α-diazo ketones. These catalysts have a mixed set of ligands that allows choosing among a big selection of ligands to gradually affect the electronic and steric properties of the catalyst. Their selectivity depends on the electrophilicity of the ligands and the polarizability of the metalated aromatic rings. Thus, Rh2(OOCR)2(PC)2 compounds [PC = (C6H4)P(CH3)(C6H5), (p-CH3C6H3)P(p-CH3C6H4)2, (C6H4)P(C6H5)2; R = C3F7 or CF3] exhibit an exceptional sele…

Unusual stability of reaction intermediates in ortho-metalation reactions of dicyclohexylphenylphosphane with dirhodium(II) tetraacetate

Abstract Reaction of dirhodium(II) tetraacetate with 1 molar equivalent of dicyclohexylphenylphosphane afforded the complex [Rh 2 (μ-O 2 CCH 3 ) 3 {μ-(C 6 H 4 )PCy 2 }(CH 3 COOH) 2 ] ( 1 ) in which the phosphane ligand is coordinated to the rhodium atoms in a bridging ortho -metalated mode. As a second product, [Rh 2 (μ-O 2 CCH 3 ) 3 {μ-(C 6 H 4 )PCy 2 }(CH 3 COOH)(PhPCy 2 )] ( 2 ) was isolated from the same reaction. 2 proved to be unusually stable toward further reaction to a doubly ortho -metalated complex which has been accessible in the reaction of dirhodium(II) tetraacetate with other phosphane ligands. However, doubly ortho -metalated [Rh 2 (μ-O 2 CCH 3 ) 2 {μ-(C 6 H 4 )PCy 2 } 2 (CH…

Orthometalation reactions in trifluoroacetate dirhodium(II) compounds. Molecular structure of Rh2(O2CCF3)2[(C6H4)PPh2]2·(PPh3)2·2(C7H8)

Abstract Rh 2 (O 2 CCF 3 ) 3 [(C 6 H 4 )PPh 2 ]·(HO 2 CCF 3 ) 2 reacts with PPh 3 yielding the doubly metalated compound Rh 2 (O 2 CCH 3 ) 2− [(C 6 H 4 )PPh 2 ] 2 ·(HO 2 CCF 3 ) 2 . The reaction proceeds via a reactive intermediate with an equatorial phosphine, Rh 2 (η 2 -O 2 CCF 3 )(μ-O 2 CCF 3 ) 2 [(C 6 H 4 )PPh 2 ](PPh 3 )·(HO 2 CCF 3 ), which can also be generated in moderate yield under photochemical conditions. The structure of the PPh 3 bis-adduct Rh 2 (O 2 CCF 3 ) 2 [(C 6 H 4 )PPh 2 ] 2 ·(PPh 3 ) 2 ·2(C 7 H 8 ) has been determined by X-ray diffraction. M r =1663.27, orthorhombic, space group Fdd 2, a =41.748(9), b =21.620(5), c =17.375(5) A, V =15683(6) A 3 , Z =8, D x =1.41 g cm −3…

Configurational landscape of chiral iron(II) bis(phosphane) complexes

[EN] The reaction of a chiral [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+ ((R,R)-Me-DuPhos = (¿)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene) complex with ethers and halides is investigated by NMR techniques. From this study, it is apparent that dihydrogen ligand exchange by poorly-coordinating donor molecules, such as THF or Et2O, is feasible under mild conditions. The cis-[FeH(THF-d8){(R,R)-Me-DuPhos}2]+ complex is identified as the product in THF-d8 solution. A mixture of cis- and trans-[FeH(ether){(R,R)-Me-DuPhos}2]+ isomers is obtained after the addition of small quantities of THF or Et2O to a CD2Cl2 solution of [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+. The reaction of [FeH(¿2-H2){(R,R)-Me-DuPhos}2]+ w…

Synthesis of a New C3-Symmetric Tripodal P4-Tetradentate Ligand and Its Application to the Formation of Chiral Metal Complexes

A novel C3-symmetric tetradentate tripodal ligand with phosphorus as coordinating atoms has been synthesized in good yields. Its coordination ability through the four phosphorus atoms, three at the...

Reaction of Rh2(μ2-O2CCH3)3[μ2-(C6H4)PMePh](HO2CCH3)2 with triphenylphosphine: rearrangement of the metalated PMePh2 ligand and formation of a compound with a diphenylphosphinomethanide group in (P,C) coordination; crystal structure of [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}- {μ2-(C6H4)PPh2}(PPh3)]·2CH2Cl2

The reaction of [Rh2(μ2-O2CCH3)3{μ2-(C6H4)PMePh}] (1) in CHCl3 with one mole of PPh3 gives the two phosphine monoadducts, which are in rapid equilibrium above −40 °C. After 6 h at room temperature this mixture gives [Rh2(μ2-O2CCH32{μ2-(C6H4)PMePh}{μ2-(C6H4)PPh2}](HO2CCH3)2 (3), a doubly metalated compound with a head-to-head configuration. 1 reacts with two moles of PPh3, forming the bis-adduct 1.P2, which at 10 °C gives a mixture 3, in the form of its phosphine adduct 3.P, and [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}{μ2- (C6H4) PPh2}(PPh3)] (2). It is confirmed that 3.P is not the kinetic product in the reaction from 1.P2 to 2. The structure of [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}{μ2-(CP6H4) PPh2} (PPh3)]…

Rhodium (II) compounds with functionalized metalated phosphines as bridging ligands

Abstract The reaction of Rh2(O2CCH3)4 · 2CH3OH with the phosphine P(4-BrC6H4)2(C6H5), 2, results in the formation of the monometalated compound Rh2(O2CCH3)3[PC] · 2CH3CO2H (PC representing a metalated P(4-BrC6H4)2(C6H5)). The reaction involves selective metalation of the phosphine at one Br-substituted ring (12:1 isomer ratio). The reaction of Rh2(O2CCH3)3[(4-BrC6H3)P(4-BrC6H4)(C6H5)] · 2CH3CO2H, 4, with one additional mol of triphenylphosphine yields a mixture of two main stereoisomers Rh2(O2CCH3)2[(4-BrC6H3)P(4-BrC6H4)(C6H5)] [(C6H4)P(C6H5)2] · 2CH3CO2H, 5a and 5b, that were isolated as pure compounds. These two compounds were resolved in the corresponding M and P enantiomers as trifluoro…

A new efficient, highly dispersed, Pd nanoparticulate silica supported catalyst synthesized from an organometallic precursor. Study of the homogeneous vs. heterogeneous activity in the Suzuki-Miyaura reaction

[EN] A new Pd(0) catalyst supported on silica UVM-7 has been synthesized from the organometallic [Pd-2(mu-(C6H4) Pp(2))(2)(CH3CN)(4)](BF4)(2) precursor, characterized by the high dispersion, activity, and small size of the palladium nanoclusters fixed on the silica surface. The catalyst was tested for the Suzuki-Miyaura (SM) reaction of different 4-substitutedphenyl halides with phenylboronic acid. The kinetic study concurs with most of the catalytic action was carried out by Pd species originated by the partial solubilization of Pd immobilized on mesoporous silica. The Schmidt's analysis of differential selectivity (SADS) in several competitive SM reactions, together the STEM-HAADF and HRT…

ChemInform Abstract: Reactivity and Selectivity of ortho-Metalated Rhodium(II) Complexes in C-H Insertion Reactions of α-Diazo Compounds.

Regioselective intramolecular C−H insertion reactions of α-diazo β-keto esters and α-diazo ketones are mediated by Rh2[OOCR]4-x[PC]x (x = 1, 2; PC = ortho-metalated phosphine; R = CH3, C3F7). In particular, the intramolecular transformation of 1-diazo-5-methyl-3-propyl-2-hexanone catalyzed by Rh2[OOCCH3]2[PC]2 (PC = (C6H4)P(C6H5)2, head-to-tail (H−T) configuration) afforded only the tertiary C−H insertion product. By comparison, no C−H insertion reaction was promoted by doubly metalated complexes with a head-to-head (H−H) configuration. Rh2[OOCR]3[PC] compounds were found to be less suited for these type of reactions.

Further orthometalated dinuclear palladium(iii) compounds with bridging N,S-donor ligands

New dinuclear palladium(III) compounds of general formula Pd2[(C6H4)PPh2]2[N-S]2Cl2, N-S being 2-mercaptopyridinate, 3a; 2-mercapto-6-methylpyridinate, 3b; 2-quinolinethiolate, 3c; 2-mercaptopyrimidinate, 3d; 1-methyl-1H-imidazole-2-thiolate, 3e; 1-methyl-1H-benzimidazole-2-thiolate, 3f; 2-mercaptobenzothiazolate, 3g and 5-mercapto-1-methyltetrazolate, 3h have been obtained by oxidation with PhICl2 of the corresponding palladium(II) counterparts. The stability of the new compounds has been studied by (31)P NMR spectroscopy from 200 to 298 K. Compounds 3f-h were relatively stable until room temperature and they have been synthesized and characterized by (31)P, (1)H and (13)C NMR spectroscopy…

Synthesis of Dirhodium(II) Complexes with Several Cyclometalated Thienylphosphines

The thermal reaction of dirhodium tetraacetate with tris(3-thienyl)phosphine (3TP), diphenyl(3-thienyl)phosphine (3TPPh2), and diphenyl(2-thienyl)phosphine (2TPPh2) gives rise to mono-cyclometalated and bis-cyclometalated compounds; the latter can have a head-to-head (H−H) or head-to-tail (H−T) configuration. Bis-cyclometalated compounds with H−T configuration can be prepared in high yield under photochemical conditions or by combining irradiation with subsequent thermal treatment in acetic acid. The reactivity order of aromatic ring C−H activation is phenyl < 2-thienyl ≪ 3-thienyl, which leads to a selective activation of the thienyl ring. Thus, only one mono-cyclometalated compound is obt…

Synthesis and electrochemical study of a new doubly-metallated compound with the ferrocene-labelled phosphine PPh2(C5H4)Fe(C5H5)

Abstract Direct reaction of the metalled compound Rh 2 (μ 2 -O 2 CCH 3 ) 3 [μ 2 -(C 6 H 4 ) PPh 2 ]·(H 2 O) 2 with PPh 2 Fc [Fc = (C 5 H 4 )Fe(C 5 H 5 )] in chloroform solution yields the corresponding mono-adduct Rh 2 (O 2 CCH 3 ) 3 [(C 6 H 4 )PPh 2 ]·(PPh 2 Fc) ( 1 ), which has been characterized by 31 P NMR spectroscopy. Photochemical irradiation of 1 in chloroform gives the compound Rh 2 (μ-O 2 CCH 3 ) 2 (η 2 -O 2 CCH 3 )[μ 2 -(C 6 H 4 )PPh 2 ][PPh 2 Fc]·(H 2 O) ( 2 ) in practically quantitative yield. Compound 2 , by thermal treatment in chloroform solution, yields cleanly the doubly-metallated compound Rh 2 (μ 2 -O 2 CCH 3 ) 2 [μ 2 -(C 6 H 4 )PPhFc][μ 2 -(C 6 H 4 )PPh 2 ]·(H 2 O) 2 ( …

Enantio- and diastereocontrol in intermolecular cyclopropanation reaction of styrene catalyzed by dirhodium(II) complexes with bulky ortho-metalated aryl phosphines

Enantiomerically pure dirhodium(II) complexes with ortho-metalated p-substituted aryl phosphines have been shown to be enantio- and diastereoselective in the cyclopropanation of styrene by ethyl diazoacetate. Enantioselectivities up to 91% and diastereoselectivities up to 90% are observed for ethyl cis-2-phenylcyclopropanecarboxylate. Estevan Estevan, Francisco, Francisco.Estevan@uv.es ; Lahuerta Peña, Pascual, Pascual.lahuerta@uv.es ; Lloret Fillol, Julio, Julio.Lloret@uv.es ; Sanau Torrecilla, Mercedes, Mercedes.Sanau@uv.es ; Ubeda Picot, M Angeles, Angeles.Ubeda@uv.es ; Vila Gomez, Jaume Llorenc, Jaume.Vila@uv.es

Reactivity and Selectivity of Ortho-Metalated Rhodium(II) Complexes in C−H Insertion Reactions of α-Diazo Compounds

Regioselective intramolecular C−H insertion reactions of α-diazo β-keto esters and α-diazo ketones are mediated by Rh2[OOCR]4-x[PC]x (x = 1, 2; PC = ortho-metalated phosphine; R = CH3, C3F7). In particular, the intramolecular transformation of 1-diazo-5-methyl-3-propyl-2-hexanone catalyzed by Rh2[OOCCH3]2[PC]2 (PC = (C6H4)P(C6H5)2, head-to-tail (H−T) configuration) afforded only the tertiary C−H insertion product. By comparison, no C−H insertion reaction was promoted by doubly metalated complexes with a head-to-head (H−H) configuration. Rh2[OOCR]3[PC] compounds were found to be less suited for these type of reactions.

Synthesis, Reactivity, and X-ray Crystallographic Characterization of Mono-, Di-, and Tetranuclear Palladium(II)-Metalated Species

The reactivity of the tetranuclear metallated palladium compound (Pd[mu 2-(C6H4)PPh2]Br)4 (1) with different ligands has been investigated with the aim of evaluating the influence of the entering ligand on the nature of the reaction products. The results confirmed the ability of the ligand [(C6H4)PPh2]- to expand a bridging [mu 2-] or a chelating [eta 2-] coordination mode, depending on the auxiliary ligands present in the complex. Bulky phosphines stabilize mononuclear species of formula (Pd[eta 2-(C6H4)PPh2]Br[P]), with a four-atom metallocycle, while small phosphines give dinuclear compounds. The molecular structures of three different metalated palladium compounds have been determined b…

New Dinuclear Catalysts Rh2(N−O)2[(C6H4)P(C6H5)2]2 with Imidate Ligands:  Synthesis and Isomerization from Head-to-Tail to Head-to-Head Configuration of the Imidate Ligands

Two new dirhodium(II) catalysts of general formula Rh(2)(N-O)(2)[(C(6)H(4))P(C(6)H(5))(2)](2) (N-O = C(4)H(4)NO(2)) are prepared, starting from Rh(2)(O(2)CCH(3))(2)(PC)(2)L(2) [PC = (C(6)H(4))P(C(6)H(5))(2) (head-to-tail arrangement); L = HO(2)CCH(3)]. The thermal reaction of Rh(2)(O(2)CCH(3))(2)(PC)(2).L(2) with the neutral succinimide stereoselectively gives one compound that according to the X-ray structure determination has the formula Rh(2)(C(4)H(4)NO(2))(2)[(C(6)H(4))P(C(6)H(5))(2)](2) (1). It corresponds to the polar isomer with two bridging imidate ligands in a head-to-head configuration. However, stepwise reaction of Rh(2)(O(2)CCH(3))(2)(PC)(2).L(2) with (CH(3))(3)SiCl and potassiu…

Spectroscopic, magnetic, and electrochemical studies of a dimeric N-substituted-sulfanilamide copper(II) complex. X-ray and molecular structure of the Cu2(N-(pyridin-2-yl)biphenyl-4-sulfonamidate)4 complex

Abstract A dinuclear copper(II) complex with a N-substituted sulfonamide as ligand has been investigated. The new N-(pyridin-2-yl)biphenyl-4-sulfonamide ligand has been prepared and structurally characterized. The copper(II) complex has been synthesized and its crystal structure, magnetic properties and EPR spectra were studied in detail. The metal centers are bridged by four nonlinear triatomic NCN groups. The coordination geometry of the copper(II) ions in the dinuclear entity is distorted square planar with two N-pyridyl and two N-sulfonamido atoms. Magnetic susceptibility data show a moderate antiferromagnetic coupling, with −2 J = 284 cm−1. The EPR spectrum of the polycrystalline sampl…

Stability of Dinuclear Phosphane Palladium(III) Complexes: A DFT Approach

Computational density functional theory studies have been carried out for the dinuclear ortho-metalated palladium(III) compounds [Pd2{μ-(C6H4)PPh2}2{μ-(X1-X2)}2Cl2]. These studies have shown that the electronic and steric properties of the auxiliary ligands (X1-X2 = bridging (carboxylato) or chelating (phenolato/acetylacetonato) O,O-donor ligands, bridging N,N-donor ligands (triazenido/formamidinato/pyrazolato), and bridging N,S-donor ligands) lead to systematic trends in their stability, highlighting that (a) the electronic nature of the donor atoms trans to the P has a clear trend, the replacement of hard donor atoms (O, N) by softer S donors generally reducing the stability of the compou…

Reaction of Tris(2-thienyl)phosphine with Dirhodium(II) Acetate. Orthometalation of a Heteroaromatic π-System and an Unusual Ring Rearrangement

The reaction of tris (2-thienyl)phosphine (1) with dirhodium(II) acetate in a 9:1 refluxing toluene/ acetic acid mixture for 2 h leads to the formation of two metalated compounds. The structure of one of them contained two new orthometalated phosphines in a head-to-head arrangement, and, surprisingly, the metalated thiophene rings, but not the nonmetalated ones, were rearranged to a 3-thienyl structure. Both types of dirhodium compounds were assessed in a catalytic α-diazo ester transformation.

Zinc complexation to N-substituted sulfonamide ligands. Preparation, properties and crystal structure of copper(II) doped ?[Zn(sulfamethizolate)2(py)]·H2O?∞

Abstract The single crystal structure and spectroscopic properties of the copper(II) doped {[Zn(sulfamethizolate) 2 (py)]·H 2 O} ∞ are reported. The complex is a polymer where the Zn(II) ions are coordinated by four N atoms in a very distorted tetrahedral environment. The sulfamethizolate anion acts as a monodentate ligand through the thiadiazole N atom and as a bridging ligand via the amino and thiadiazole N atoms. The compound is studied by EPR, by 13 C NMR in solid state and by 1 H and 13 C NMR in DMSO-d 6 solution. The similarity between the 13 C NMR spectrum in solution and the solid 13 C NMR spectrum indicates that the structure of the compound remains in solution. The EPR spectrum sh…

Effect of thermal treatment on the structural evolution of 3:2 and 2:1 mullite monophasic gels

Abstract Single phase mullite gels with composition 3Al2O3 · 2SiO2 (3:2) and 2Al2O3 · SiO2 (2:1) were prepared by the semialkoxide method using aluminum nitrate nonahydrate and tetraethylorthosilicate as reagents. The influence of the thermal processing conditions on the reaction sequence was investigated. Both 3:2 and 2:1 mullite gels formed orthorhombic mullite under fast heating (40 °C/min) at 900 °C. Slow heatings delayed the formation of mullite in both gel compositions but no formation of spinel was detected between 1000 °C and 1100 °C. The slow transformation of pentacoordinated aluminum to octahedral and tetrahedral arrangements probably depends on the larger size and extent of the …

High yield synthesis of trinuclear [M3S4X3(diphos)3]+ (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) molecular clusters from solid state materials. Synthesis and structure of [W3S4H3(dppe)3](BPh4)

The excision of polymeric {M 3 S 7 X 4 } x (M=Mo, W; X=Cl, Br) cluster phases with diphosphines (dmpe, dppe) in acetonitrile affords a one step general synthetic route for the preparation of trinuclear molecular clusters with formula [M 3 S 4 X 3 (diphos) 3 ] + (M=Mo, W; X=Cl, Br and diphos=dmpe, dppe) in high yields. Following this strategy, the cluster cations [Mo 3 S 4 Br 3 (dmpe) 3 ] + and [W 3 S 4 Br 3 (dppe) 3 ] + have been prepared for the first time. This last tungsten cluster has proved to be a useful synthon for the synthesis of the hydride derivative [W 3 S 4 H 3 (dppe) 3 ] + in moderate yields. The crystal structure of [W 3 S 4 H 3 (dppe) 3 ](BPh 4 ) consists of a equilateral tu…

Benzoato and Thiobenzoato Ligands in the Synthesis of Dinuclear Palladium(III) and ‐(II) Compounds: Stability and Catalytic Applications

New palladium(III) compounds of formula Pd2[(C6H4)PPh2]2[OXC(C6H5)]2Cl2 [3a (X = O); 3b (X = S)] were obtained by the oxidation of the analogous palladium(II) ones with PhICl2 and were characterized by 31P, 1H, and 13C NMR spectroscopy at 223 K. Compound 3a was also structurally characterized by single-crystal X-ray diffraction methods, which revealed a Pd–Pd distance of 2.5212(10) A. DFT calculations were conducted to study the stability of all of these new palladium(III) and -(II) compounds with focus on the influence of the OS substitution of the donor atom in the ligand. The palladium(II) compounds Pd2[(C6H4)PPh2]2[OXC(C6H5)]2 [2a (X = O), 2b (X = S)] were also tested as precatalyst in …

Synthesis of Cyclometalated Rhodium(III) Complexes. Study of the Carbonyl Insertion Reactions into the Rh-C Bond of the Metalocycle

Abstract In this paper we report the preparation of new orthometalated rhodium(III) compounds of the formula Rh(oq)(AB)(PC), from Rh(oq)(Br)(PC)(H20), AB being a bidentade anionic ligand, oq= 8-oxyquinolate and PC = P(o-C6F4)Ph2. Their redox behaviour is also described. The reaction of Rh(Oq)(Br)(PC)(H20) [Oq = 5-Me-8-oxyquinolate (5-Meoq), 8-oxyquinolate] with carbon monoxide under pressure leads to expansion of the metalocycle ring by CO insertion into the Rh-C bond.

Synthesis, Structure, and Reactivity of (Dihydrogen)(hydrido)iron(II) Complexes Bearing Chiral Diphos­phanes

The heterolytic cleavage of molecular hydrogen by [Fe(H2O)6][BF4]2 and the chiral phosphane (+)-1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene [(R,R)-Me-DuPhos] or its enantiomer [(S,S)-Me-DuPhos] yields the (dihydrogen)(hydrido)iron complexes [FeH(2-H2){(R,R)-Me-DuPhos}2]BF4 ([R,R-1]BF4) and [FeH(2-H2){(S,S)-Me-DuPhos}2]BF4 ([S,S-1]BF4), respectively. These complexes are fluxional in solution at room temperature, and the trans isomers are observed at 200 K. The ()-cis-[R,R-1]BF4 complex was identified crystallographically as the only stereoisomer at room temperature. The energetic and structural differences between the cis ( and ) and trans isomers were analyzed from a computational (DFT)…

Synthesis and structure of the incomplete cuboidal clusters [W3Se4H3(dmpe)3]+, [W3Se4H3−x(OH)x(dmpe)3]+and [W3Se4(OH)3(dmpe)3]+, and the mechanism of the acid-assisted substitution of the coordinated hydrides

The novel incomplete cuboidal cluster [W3Se4H3(dmpe)3](PF6), [1](PF6), has been prepared by reduction of [W3Se4Br3(dmpe)3](PF6) with LiBH4 in THF solution. The trihydroxo complex [W3Se4(OH)3(dmpe)3](PF6), [2](PF6), was obtained by reacting [W3Se4Br3(dmpe)3](PF6) with NaOH in MeCN–H2O solution. The complexes [1](PF6) and [2](PF6) were converted to their BPh4− salts by treatment with NaBPh4. Recrystallisation of [1](BPh4) in the presence of traces of water affords the mixed dihydride hydroxo complex [W3Se4H2(OH)(dmpe)3](BPh4). The crystal structures of [1](BPh4), [2](BPh4) and [W3Se4H2(OH)(dmpe)3](BPh4) have been resolved. Although the [1]+ trihydride does not react with an excess of halide s…

Photoinduced and Self‐Activated Nuclease Activity of Copper(II) Complexes with N ‐(Quinolin‐8‐yl)quin­olin‐8‐sulfonamide – DNA and Bovine Serum Albumin Binding

Two CuII complexes with a new quinoline sulfonamide derivative and phenanthroline (phen), [Cu(QSQ)(phen)]ClO4·0.5H2O (1) and [Cu(QSQ)(phen)(H2O)]ClO4 (2) [HQSQ = N-(quinolin-8-yl)quinolin-8-sulfonamide], have been synthesized and physicochemically characterized. Single-crystal X-ray diffraction studies have revealed a highly distorted trigonal-bipyramidal structure for 1 (τ = 0.68) and an almost perfect trigonal-bipyramidal geometry for 2 (τ = 0.92). DNA binding studies, which were performed by thermal denaturation, viscometry, fluorescence spectroscopy, and cyclic voltammetry, indicated a partial intercalation of 1 with Kapp = 2.45 × 106 M–1. The nuclease activity of 1 was investigated upo…

Analysis of the main structural trends for biscyclometalated dinuclear rhodium compounds with nitrogen donor axial ligands

A new series of biscyclometalated dinuclear rhodium(II) compounds with the general formula Rh 2 (O 2 CR) 2 (PC) 2 · (N) 2 have been obtained, where PC is a cyclometalated phosphine, R an aliphatic group, and N a nitrogen donor ligand. The crystal structures for these compounds have been determined by X-ray diffraction. The most important structural trends have been analyzed, and have also been compared with the same parameters for different analogous compounds described previously in the literature.

AC3-Symmetric Palladium Catalyst with a Phosphorus-Based Tripodal Ligand

ortho-Metalated Dirhodium(II) Catalysts Immobilized on a Polymeric Cross-Linked Support by Copolymerization. Study of their Catalytic Activity in the Asymmetric Cyclopropanation of Styrene with Ethyl Diazoacetate

Chiral ortho-metalated dirhodium(II) compounds containing the phosphine P(p-CH2═CHC6H4)3 have been efficiently immobilized by radical copolymerization with styrene and 1,4-divinylbenzene. Their cat...

An Unprecedented Iridium(III) Catalyst for Stereoselective Dimerisation of Terminal Alkynes

A novel iridium(III) hydride complex, IrHCl(TIMP 3 ) {HTIMP 3 = tris[1-(diphenylphosphino)-3-methyl-lH-indol-2-yl]methane) was prepared and fully characterized in both the solid state and in solution. Chloride abstraction by silver cations provides a more reactive compound, [IrH-(TIMP 3 )][BF 4 ], which can react with pyridine (py) and phenylacetylene to yield the complexes [IrH-(TIMP 3 )(py)][BF 4 ] and [Ir(PhCH=C-CH=CHPh)-(TIMP 3 )][BF 4 ], respectively. Interestingly, IrH-(TIMP 3 )(py)][BF 4 ] efficiently catalyses the stereoselective dimerisation of model terminal alkynes to the 1,4-disubstituted (E)-but-1-en-3-yne only.

Pyrazole and Pyrazolate as Ligands in the Synthesis and Stabilization of New Palladium(II) and (III) Compounds.

The versatility of pyrazole/pyrazolate as ligands has allowed the synthesis and the structural characterization of four different types of new orthometalated palladium compounds, for which DFT calculations have been performed in order to investigate their relative stabilities. [Pd2{μ-(C6H4)PPh2}2{μ-(R,R'2pz)}2] (R = R' = H, 2a; R = Br, R' = H, 2b; R = CH3, R' = H, 2c; R = H, R' = CH3, 2d; R = Br, R' = CH3, 2e) compounds with exo-bidentate pyrazolatos are the first paddlewheel dinuclear palladium(II) compounds with pyrazolato bridging ligands described and characterized in the literature. In the process of the synthesis of 2a, a new tetranuclear intermediate compound, [Pd4{μ-(C6H4)PPh2}4(μ-p…

Dinuclear Ortho-Metalated Palladium(II) Compounds with N,N- and N,O-Donor Bridging Ligands. Synthesis of New Palladium(III) Complexes

New dinuclear ortho-metalated palladium(II) compounds with N,N′-diarylformamidinates, Pd2[(C6H4)PPh2]2[R′NC(H)NR′]2 (R′ = C6H5, 3a; R′ = p-CH3C6H4, 3b; R′ = p-CH3OC6H4, 3c) and N,O-donor ligands, Pd2[(C6H4)PPh2]2[N,O]2 (N,O = succinimidate (5), phtalimidate (6), 2-hydroxypyridinate (7), acetanilidate (8)) have been synthesized and characterized by NMR spectroscopy and X-ray diffraction methods. The oxidation with iodobenzene dichloride gave new and rare Pd26+ compounds, Pd2[(C6H4)PPh2]2[R′NC(H)NR′]2Cl2 (R′ = C6H5, 4a; R′ = p-CH3C6H4, 4b). DFT calculations on the Pd24+ → Pd26+ oxidation reaction show that the substituents on the amidinate N atoms have a greater effect on the reaction energy …

Preparation and study of silver maleonitriledithiolate complexes

Abstract This paper reports the reaction of Ag2(mnt) and [(NEt4)Ag(mnt)] (mnt2− = maleonitriledithiolate) with PPh3 and 1,2-bis(diphenylphosph

Synthesis and X-ray structure of metalated Rhodium(II) catalysts with a chiral phospholane

The reaction of Rh2(O2CR)4 (R = CH3, CF3) with the chiral phosphane (2S,5S)-2,5-dimethyl-1-phenylphospholane (PC*H), results in the formation of two diastereoisomers of Rh2(O2CCR)2(PC*)2, with (P) and (M) configuration. These can easily be isolated by chromatographic methods to obtain enantiomerically pure RhII compounds. Preliminary catalytic studies have shown that they induce moderate asymmetry in the cyclization of 5-aryl-1-diazo-2-pentanones and 1-diazo-5-hexen-2-one. X-ray analysis of the (M) diastereoisomer with formula Rh2(O2CCCH3)2(PC*)2 is reported. The crystallographic parameters are as follows: space group P21212 (orthorhombic) with a = 12.1347(11) A, b = 14.5870(13) A, c = 9.81…

CCDC 1501673: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 996516: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 944605: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 944602: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1052931: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Susana Ibáñez, Albert Ofori, Pipsa Hirva, Mercedes Sanaú and Ma Angeles Úbeda|2015|Eur.J.Inorg.Chem.||2822|doi:10.1002/ejic.201500324

CCDC 1501676: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1407215: Experimental Crystal Structure Determination

Related Article: Alejandro Pascual-Álvarez, Tamara Topala, Francisco Estevan, Francisca Sanz and Gloria Alzuet-Piña|2016|Eur.J.Inorg.Chem.||982|doi:10.1002/ejic.201501469

CCDC 996514: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 941941: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 941943: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 916484: Experimental Crystal Structure Determination

Related Article: Konrad Herbst, Mercedes Sanaú, Francisco Estevan, M. Angeles Úbeda|2013|J.Organomet.Chem.|733|53|doi:10.1016/j.jorganchem.2013.02.030

CCDC 996519: Experimental Crystal Structure Determination

Related Article: Susana Iba��ez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sana��, Ma Angeles ��beda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 944603: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1501675: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 941946: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 1419794: Experimental Crystal Structure Determination

Related Article: Marta Feliz and Francisco Estevan|2016|Eur.J.Inorg.Chem.||92|doi:10.1002/ejic.201501085

CCDC 1501674: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1823385: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 941945: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 944600: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 941947: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 1823543: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1952457: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Marta Feliz|2020|Dalton Trans.|49|4528|doi:10.1039/C9DT04821A

CCDC 1052933: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Susana Ibáñez, Albert Ofori, Pipsa Hirva, Mercedes Sanaú and Ma Angeles Úbeda|2015|Eur.J.Inorg.Chem.||2822|doi:10.1002/ejic.201500324

CCDC 941942: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 941944: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D

CCDC 996518: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 1952454: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Marta Feliz|2020|Dalton Trans.|49|4528|doi:10.1039/C9DT04821A

CCDC 996517: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 1952455: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Marta Feliz|2020|Dalton Trans.|49|4528|doi:10.1039/C9DT04821A

CCDC 944604: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1952456: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Marta Feliz|2020|Dalton Trans.|49|4528|doi:10.1039/C9DT04821A

CCDC 1052932: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Susana Ibáñez, Albert Ofori, Pipsa Hirva, Mercedes Sanaú and Ma Angeles Úbeda|2015|Eur.J.Inorg.Chem.||2822|doi:10.1002/ejic.201500324

CCDC 996515: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 996520: Experimental Crystal Structure Determination

Related Article: Susana Ibañez, Larisa Oresmaa, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, Ma Angeles Úbeda|2014|Organometallics|33|5378|doi:10.1021/om500702j

CCDC 944601: Experimental Crystal Structure Determination

Related Article: Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, MaAngeles Úbeda|2018|Organometallics|37|2980|doi:10.1021/acs.organomet.8b00342

CCDC 1407214: Experimental Crystal Structure Determination

Related Article: Alejandro Pascual-Álvarez, Tamara Topala, Francisco Estevan, Francisca Sanz and Gloria Alzuet-Piña|2016|Eur.J.Inorg.Chem.||982|doi:10.1002/ejic.201501469

CCDC 941940: Experimental Crystal Structure Determination

Related Article: Susana Ibáñez, Doris Nena Vrečko, Francisco Estevan, Pipsa Hirva, Mercedes Sanaú, M a Angeles Úbeda|2014|Dalton Trans.|43|2961|doi:10.1039/C3DT52717D