Etherification of Functionalized Phenols with Chloroheteroarenes at Low Palladium Loading: Theoretical Assessment of the Role of Triphosphane Ligands in CO Reductive Elimination

The present study highlights the potential of robust tridentate ferrocenylphosphanes with controlled conformation as catalytic auxiliaries in CO bond formation reactions. Air-stable palladium triphosphane systems are efficient for selective heteroaryl ether synthesis by using as little as 0.2 mol% of catalyst. These findings represent an economically attractive and clean etherification of functionalized phenols, electron-rich, electron-poor and para-, meta- or ortho-substituted substrates, with heteroaryl chlorides, including pyridines, hydroxylated pyridine, pyrimidines and thiazole. The etherification tolerates very important functions in various positions, such as cyano, methoxy, amino, …

Direct subphthalocyanine conjugation to bombesin vs. indirect conjugation to its lipidic nanocarrier

International audience; Bombesin (BBN) was covalently bound to graftable subphthalocyanine (SubPc) or to a cholesterol derivative, a component of a liposome that encapsulates non-graftable SubPc. The latter bioconjugation approach was suitable to address the stability of SubPc and was achieved by copper-free click-chemistry on the outer-face of the liposome. Liposomes were purified (FPLC) and then analyzed in size (outer diameter about 60 nm measured by DLS). In vitro binding studies allowed to determine the IC50 13.9 nM for one component of the liposome, cholesterol, conjugated to BBN. Hence, azido- (or alkynyl-) liposomes give fluorophores with no reactive functional group available on th…

Exploring reactivity of a bis-sulfonium zirconocene-ate dimer: synthesis of various zwitterionic phosphonium anionic zirconocene complexes

Abstract Formal [3+2] cycloaddition reactions between the bis-sulfonium zirconocene-ate dimer 1a and methylpropiolate, benzaldehyde and carbon disulfide afforded stable zwitterionic phosphonium zirconocene-ate complexes 2–4, respectively, with two orthocondensed five-membered heterocycles. X-ray crystal structure of 4 has been determined. Elemental chalcogens (S, Se, Te) gave rise also to a new variety of five-coordinate zirconium(IV) complexes (5–7) by a formal [3+1] cycloaddition reaction. In these bicyclic zirconates, sulfur is included in a five-membered ring while the second chalcogen is in a four-membered one.

Synthesis of β-P,N Aminophosphines and Coordination Chemistry to PdII. X-ray Structures of [PdCl2(Ph2PCH2CH(Ph)NHPh-κP,κN)] and [PdCl(η3-C3H5)(Ph2PCH2CH(Ph)NHPh-κP)]

The reaction of the CN bond in PhCHNPh with the carbanionic species Ph2PCH2-, leading to the N-phenyl β-aminophosphine Ph2PCH2CH(Ph)NHPh, L1, is described. This molecule reacts with different organ...

New heteronuclear gold(I)-platinum(II) complexes with cytotoxic properties: are two metals better than one?

A series of mono- and heterodinuclear gold(I) and platinum(II) complexes with a new bipyridylamine-phosphine ligand have been synthesized and characterized. The X-ray structures of the ligand precursor 4-iodo-N,N-di(pyridin-2-yl)benzamide, and of one gold derivative are reported. All the complexes display antiproliferative properties in vitro in human cancer cells in the range of cisplatin or higher, which appear to correlate with compounds' uptake. Interestingly, studies of the interactions of the compounds with models of DNA indicate different mechanisms of actions with respect to cisplatin. The biological activity study of these complexes provides useful information about the interest of…

Reactivity of di-tert-butyldimethoxystannane with carbon dioxide and methanol: X-ray structure of the resulting complex

Abstract The synthesis of dimethyl carbonate from carbon dioxide and methanol was studied with ditert-butyldimethoxystannane under pressure at temperatures ⩽423 K. The formation of dimethyl carbonate is accompanied by transformation of the stannane into a trinuclear complex, the structure of which has been determined by single-crystal X-ray diffraction technique. The relevance of this specie in the catalytic cycle is demonstrated by conducting recycling runs. A preliminary kinetic study underlines the steric influence of the tert-butyl ancillary ligands in the stabilisation of intermediates, by comparison with the n-butyl homologue.

New Insights into the Stoichiometric and Catalytic Reactivity of Unsaturated Pd 3 (dppm) 3 CO n + Clusters ( n = 0, 1) Towards Halocarbons – First Evidence for Inorganic By‐Products

The title clusters, Pd 3 (dppm) 3 (CO) + and Pd 3 (dppm) 3 (CO) 0 can be electrochemically generated from the 1- and 2-electron reductions, respectively, of the Pd 3 (dppm) 3 (CO) 2 + cluster [dppm = bis(diphenylphosphanyl)methane; Pd 3 2 + ]. Pd 3 + reacts in a stoichiometric ratio with methyl iodide, MeI, and benzyl bromide, BzBr, in THF to provide the corresponding Pd 3 (X) + adducts (X = I, Br respectively) as inorganic products. Other products are Bz 2 and PhMe for BzBr but, for MeI, no organic product was observed (since they are too volatile). In the presence of the same substrates, Pd 3 0 also reacts in a stoichiometric ratio to form the same organics and the Pd 3 -(X) + adducts (X …

Resolution of β-aminophosphines with chiral cyclopalladated complexes

Abstract Resolution of the racemic chiral β-aminophosphines Ph 2 PCH 2 CH(Ph)NH(Ar) ( L 1 for Ar = C 6 H 5 and L 2 for Ar = 2,6-C 6 H 3 i Pr 2 ) has been investigated by use of different cyclopalladated complexes as chiral agents. The resulting complexes afford diastereomeric adducts in a 1:1 ratio. After successive crystallizations from ethanol, a d.e. of 98% was achieved for one aminophosphine palladium complex, while no significant d.e. was obtained after crystallizations from chlorinated solvents. The X-ray structure analysis has pointed out intermolecular hydrogen interactions N–H⋯Cl between the P,N ligand and the chloride ion, which are responsible for the formation and stabilization …

Oxo and Hydroxo Tantalocene Complexes:  Synthesis and Reactivity. X-ray Molecular Structures of [(η5-Cp*)TaCl(OH)(η5-C5H4SiMe3)]+Cl-, (η5-Cp*)TaCl(O)(η5-C5H4SiMe3), and [(η5-Cp*)TaCl2(η5-C5H4SiMe3)]+PF6-

Exposure of a THF solution of tantalocene dichloride complexes (η 5 -Cp*)TaCl 2 (η 5 -C 5 H 4 -SiMe 3 ) (1) and (η 5 -Cp*)TaCl 2 (η 5 -C 5 H 5 ) (2) to the ambient atmosphere for 12 h leads to the formation of new tantalum(V) cationic hydroxo complexes [(η 5 -Cp*)TaCl(OH)(η 5 -C 5 H 4 SiMe 3 )] + -Cl- (3) and [(η 5 -Cp*)TaCl(OH)(η 5 -C 5 H 5 )]+Cl - (4). This oxidation reaction is more rapid under oxygen atmosphere since the hydroxo complexes are obtained in better yields within only 15 min. The hydroxo complexes are easily deprotonated by base to generate oxo complexes 5 and 6, which, in turn, react with trimethylsilyl triflate, giving the corresponding cationic silylated complexes 7 and 8…

Cost efficient preparation of lead aminoalkoxides directly from lead(II) oxide

Abstract The preparation of lead(II) aminoalkoxides has been demonstrated from the direct reaction of aminoalcohols with lead(II) oxide. The denticity of the aminoalcohols determined the facility of the reactions, the rate increasing with the number of hydroxyls. Thus, [Pb(dmae)2], 1, [Pb(mdea)]∞, 2, and [Pb(teaH)]2, 3 (dmaeH = dimethylaminoethanol, mdeaH2 = N-methyldiethanolamine, and teaH3 = triethanolamine) have been prepared in high yields and characterized by 1H and 13C NMR. The X-ray crystal structure analyses of 2 and 3 are described.

Synthesis, Coordination to Rh(I), and Hydroformylation Catalysis of New β-Aminophosphines Bearing a Dangling Nitrogen Group:  An Unusual Inversion of a Rh-Coordinated P Center

Variants of the beta-aminophosphine L(1) [Ph(2)PCH(2)CH(Ph)NHPh] containing additional nitrogen donor functions have been prepared. These functions are branched off the C atom adjacent to the P atom, or the P atom itself. Ligand [Ph(2)PCH(o-C(6)H(4)NMe(2))CH(Ph)NHPh] has been obtained as a mixture of two diastereomers L(3A) and L(3B) by lithiation of L(2) [Ph(2)PCH(2)(o-C(6)H(4)NMe(2))] with n-BuLi followed by PhCH=NPh addition and hydrolysis. The diastereomers have been separated by fractional crystallization from ethanol. Ligand Et(2)NCH(2)P(Ph)CH(2)CH(Ph)NHPh has been obtained as a mixture of two diastereomers L(5A) and L(5B)(starting with P-Ph reductive cleavage of L(1) by lithium and s…

Synthesis and X-ray structure of cationic β-diimine palladium complexes containing π-methallyl ligand

High yield of cationic palladium β-diimine complexes [(CH 2 (MeCNAr) 2 )Pd(η 3 -C 4 H 7 )][Y] (Ar = C 6 H 5 , Y = PF 6 (8); 2-Me-C 6 H 4 , Y = PF 6 (9); 2,6-Me 2 -C 6 H 3 , Y = PF 6 (10); 2,6-iPr 2 -C 6 H 3 , Y = PF 6 (11), Y = B(3,5-(CF 3 ) 2 -C 6 H 3 ) 4 (12)) have been obtained by an oxidative addition of the methallyloxyphosphonium salts (5, 6) to a preformed complex Pd(dba) 2 (7) in the presence of the β-iminoamine ligands (1-4). These complexes are thermally stable and have been characterized by 'H and 1 3 C{ 1 H} NMR as well as IR spectroscopy. The structure of the cationic allyl palladium complex (12) has been solved by X-ray crystallography.

Modular P-Chirogenic Aminophosphane-Phosphinite Ligands for Rh-Catalyzed Asymmetric Hydrogenation: A New Model for Prediction of Enantioselectivity

An original series of P-chirogenic aminophosphane-phosphinite (AMPP) ligands has been synthesized from (+)- or(–)-ephedrine in 23 to 61 % overall yields by a versatile three-step methodology. The AMPP ligands, bearing either one or two P-chirogenic centers, were used in the form of rhodium complexes for the catalyzed hydrogenation of α-acetamidocinnamate as a test reaction. Notably, even with AMPP ligands all derived from (+)-ephedrine, variation of the substituent on a P-center allowed the phenylalanine derivatives to be obtained in either (S) or (R) absolute configurations, with ee values ranging from 99 % (S) to 88 % (R). The asymmetric induction was analyzed with the aid of X-ray struct…

Straightforward Synthesis of Donor‐Stabilised Phosphenium Adducts from Imidazolium‐2‐carboxylate and Their Electronic Properties (Eur. J. Inorg. Chem. 31/2007)

The cover picture shows one of donor-stabilized phosphenium compounds which have been obtained by direct addition of chlorophosphanes to the 1,3-dimethylimidazolium-2-carboxylate without any further purification step. Their stronger κ-acceptor character similar to phosphites and their ionic nature render these ligands very promising in the development of new continuous-flow catalytic processes. Details of phosphorylation mechanisms of imidazolium-2-carboxylate as well as the electronic and steric properties of these adducts are discussed in the article by J. Andrieu et al. on p. 4877 ff.

Gold(I)-Coumarin-Caffeine-Based Complexes as New Potential Anti-Inflammatory and Anticancer Trackable Agents.

Three new gold(I)-coumarin-based trackable therapeutic complexes and two non-trackable analogues have been synthesised and fully characterised. They all display anti-proliferative properties on several types of cancer cell lines, including those of colon, breast, and prostate. Two complexes displayed significant anti-inflammatory effects; one displayed pro-inflammatory behaviour; this highlights the impact of the position of the fluorophore on the caffeine scaffold. Additionally, the three coumarin derivatives could be visualised in vitro by two-photon microscopy.

Different coordination modes of a 1,1′,2,2′-ferrocenyltetraphosphine: Bi- and tri-dentate behaviour with group 6 and 7 transition metals

The behaviour of 1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di(tert-butyl)ferrocene (1), acting as a homoannular or heteroannular ligand, has been studied. Due to the cisoid disposition of the phosphino groups of each ring, different coordination modes are observed. With group 6 metal carbonyls, M(CO)6, the tetraphosphine acts exclusively as a tridentate ligand. In contrast, the reaction with MnCp(CO)3 leads to complexes showing 1,1′ and 1,2 bidentate coordination modes. All these complexes have been characterised by 1H and 31P NMR spectroscopy. The molecular structures of the molybdenum complex [(1)Mo(CO)3] (2b) and the 1,1′ manganese complex [(1)MnCp(CO)] (3) have been established by X-ra…

Bimetallic complexes with ruthenium and tantalocene moieties: Synthesis and use in a catalytic cyclopropanation reaction

Abstract The reaction of the tantalocene dichloride monophosphines ( 1 – 2 ) with the binuclear complex [( p -cymene)RuCl 2 ] 2 gives the heterobimetallic compounds ( p -cymene)[(η 5 -C 5 H 5 )(μ-η 5 :η 1 -C 5 H 4 (CH 2 ) 2 PR 2 )TaCl 2 ]RuCl 2 ( 3 – 4 ). The air oxidation of these bimetallic species 3 – 4 , leads to the cationic hydroxo tantalum ruthenium derivatives 5 – 6 . The last ones are easily deprotonated by a base to afford the oxo analogues 7 – 8 . A preliminary assessment in catalytic cyclopropanation of styrene with tantalum ruthenium bimetallic complexes 3 – 8 as precatalysts revealed a cooperative effect with a subtle role of the early metal fragment.

Chiral α-P,N Ligands From a Diastereoselective Ph2PH Addition to (η6-Benzaldimine)tricarbonylchromium Complexes

International audience; Chiral α-aminophosphane (α-P–C–N) ligands have been prepared by reversible addition of Ph2PH to tricarbonylchromium benzaldimine complexes (CO)3Cr[η6-o-C6H4(Y)(CH=NR)] (with Y, R = CH3, CH3 or CH2COOCH3; CH3O, CH3 or p-CH3OC6H4; Cl, C6H5), with complete diastereoselectivity. These complexes are stabilized in solution by electron-withdrawing group(s) on the imine.

High oxidation state aqueous organometallics: synthesis and structure of a dinuclear oxo(pentamethylcyclopentadienyl)acetato complex of molybdenum(IV), [Cp*Mo(μ-O)(μ-O2CCH3)]2

International audience; The zinc reduction of Cp*2Mo2O5 in a MeOH–H2O mixture in the presence of acetic acid affords the diamagnetic dinuclear compound [Cp*MoO(O2CCH3)]2. An X-ray structural investigation reveals a novel dioxo- and diacetato-bridged structure, with a relatively strong metal–metal bond [2.5524(3) Å]. The compound exhibits a reversible one-electron oxidation process in the cyclic voltammogram. A comparison with other related structures reveals the effect of the electric charge on the mononuclear or dinuclear structural choice.Zinc reduction of Cp*2Mo2O5 in water–methanol in the presence of acetic acid affords compound Cp*2Mo2O2(O2CCH3)2, whose dinuclar tetrabridged structure …

Cytoprotective and antioxidant properties of organic selenides for the myelin-forming cells, oligodendrocytes.

Abstract Here a new series of twenty-one organoselenides, of potential protective activity, were synthesized and tested for their intrinsic cytotoxicity, anti-apoptotic and antioxidant capacities in oligodendrocytes. Most of the organoselenides were able to decrease the ROS levels, revealing antioxidant properties. Compounds 5b and 7b showed a high glutathione peroxidase (GPx)-like activities, which were 1.5 folds more active than ebselen. Remarkably, compound 5a diminished the formation of the oligodendrocytes SubG1 peak in a concentration-dependent manner, indicating its anti-apoptotic properties. Furthermore, based on the SwissADME web interface, we performed an in-silico structure-activ…

"Through-space" 31P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: improvement in the determination of the distance dependence of J(P,P) constants

Abstract From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31P–31P “through-space” nuclear spin–spin coupling constants (JPP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these JPP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P⋯P distance dependence of coupling constants) is remarkably confirmed, and mathemati…

A Straightforward Route to Homoallyl-Homocrotylamines Promoted by a Titanium Complex

I�-Allyltitanium complexes, generated in situ from 1,3-dienes and Cp2TiH, react with benzotriazole derivatives to give homoallylic amines in good yields. Under similar conditions, triple cascade reactions (allyltitanation followed by cationic 2-aza-Cope rearrangement followed by a second allyltitanation) occur from bis(benzotriazolyl) compounds affording a straightforward route to homoallyl-(E)-homocrotylamines. A theoretical study provides further insight into the factors that govern the selectivity of this sequence of reactions. The titanium-promoted reductive coupling of 1,3-dienes with bis(benzotriazolyl) compounds as substrates led selectively to homoallyl-homocrotylamines through a tr…

Rhodium and palladium complexes from 1,1′ and 1,2 ferrocenylphosphine as bidentate ligands. Versatile coordination

Abstract The complexation of the mixed bidentate ligands 1-diphenylphosphino-1′-diphenylthiophosphinoferrocenyl and 1,2-bis(diphenylphosphino)ferrocenyl with rhodium(I) and palladium(II) species yield a range of mono- and dirhodium or palladium complexes. Their interest as possible catalysts for alkene hydroformylation and alkoxycarbonylation and Heck coupling reactions has been assessed. Fe[C5Me4P(S)Ph2][C5Me4PPh2]PdCl2 and Fe[C5H2-1,2-(PPh2)2-4-tBu][C5H5]PdCl2 have been characterized by single-crystal X-ray diffraction studies.

Lanthanide molecular oxohydroxides: Synthesis and characterisation of [Y4(μ4-O)(μ-OEt)2(μ,η2-AAA)2(η2-AAA)3]2(μ3-OH)4(μ3-OEt)2 (HAAA = allylacetatoacetate)

International audience; The reaction between Y5O(OPri)13 and allylacetatoacetate or 2-(methacryloyloxy)ethyl acetatoacetate in 1:5 stoichiometry afforded octanuclear oxohydroxo species. Structural characterization was achieved for the allylacetatoacetate derivative homo and copolymerisation reactions with styrene were evaluated for doping of polystyrene. Hydoxo species, Y4(OH)2(AAA)10, where also obtained by reacting Y[N(SiMe3)]3 and HAAA.

Proline-Modified Porphyrin Catalysts for Enantioselective Epoxidations: Design, Synthesis, and Reactivity

International audience; The syntheses of various strapped and −picket-fence× chiral porphyrins are described, and their reactivities towards the enantioselective epoxidation of alkenes are reported. Four L-proline residues provide the chiralityfor the various meso-substituted catalysts, which differ by either the spatial arrangement of the stereogenic centers or the nature and length of the straps. The resulting bridged structures possess four amide linkages ineach strap, leading to highly rigid molecules with well-defined geometries whereas the strapped Fe catalysts gave rise to only moderate enantioselectivities, the C2-symmetrical ones being superior to the D2-symmetrical compounds. The …

Redefinition of the kilogram in 2018

Versatile behavior of conjugated diynes with zirconocene reactive species

Thermal decomposition of Cp2ZrPh2 in the presence of the buta-1,3-diynes RC≡CC≡CR (R = Ph, SiMe3) can lead to seven- or five-membered metallacycles. In both cases a stable benzo-fused seven-membered zirconacyclocumulene arising from a 2-fold insertion of the triple bonds of the dialkyne in the in situ generated zirconocene benzyne is formed. In the case of Me3SiC≡CC≡CSiMe3 a second minor complex is isolated: a 3-alkynyl-substituted zirconaindene arising from a β monoinsertion of one acetylenic function of the conjugated diyne in the zirconocene benzyne. No stable 2-alkynyl-substituted zirconacycle was isolated. This α monoinsertion complex is an intermediate in the exchange of the metalated…

Ti–Ru bimetallic complexes: catalysts for ring-closing metathesis

The reaction of the titanocene monophosphanes ( 1 – 4 ) with the dimer [( p -cymene)RuCl 2 ] 2 gives the heterobimetallic compounds ( p -cymene)[(η 5 -C 5 H 5 )(μ-η 5 :η 1 -C 5 H 4 (CR 2 ) n PR′ 2 )TiCl 2 ]RuCl 2 ( 5 – 8 ). The structure of 8 , determined by X-ray diffraction, is reported here. A preliminary assessment of the performance of these complexes in ring-closing metathesis (RCM) revealed an excellent Ti–Ru–allenylidene pre-catalyst 12 .

η⇌μ exchange bonding mode of bidentate tmeda ligand. Molecular structure of [Y(tmhd)3]2(μ-tmeda)

Abstract The reaction between the yttrium β-diketonate complexes Y(tmhd)3(H2O)x (x=0 or 1) and 0.5 or 1 equivalent of N,N,N′,N′-tetramethylethylenediamine (tmeda=Me2NCH2CH2NMe2) in hexane at room temperature afforded [Y(tmhd)3]2(tmeda) (1) and Y(tmhd)3(tmeda) (2) derivatives, respectively. They have been characterized by FT-IR, 1H NMR spectroscopy and by single crystal X-ray diffraction for 1. Variable temperature 1H NMR experiments indicated an equilibrium between 1 and 2. Their thermal behaviors were characterized by TGA and sublimation experiments. 2 is converted into compound 1 by heating over 100 °C. These precursors were used for the growth of Y2O3 and YBa2Cu3O7 − x films by pulsed in…

The Radical Trap in Atom Transfer Radical Polymerization Need Not Be Thermodynamically Stable. A Study of the MoX3(PMe3)3 Catalysts

The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order ClBrI) for the one-electron oxidation wave. Addition of X(-) changes the voltammogram, indicating the formation of MoX(4)(PMe(3))(3) f…

Anionic Monosubstituted Cyclopentadienylsamarium Derivatives: Catalysts for a Stereospecific Isoprene Polymerization

New alkyl and allyl complexes 1–3 {1: [Cp′2Sm(C3H5)]n, Cp′ = Me3CC5H4; 2: [Me4C2(C5H4)2]Sm(C3H5)2Li(dme),dme = (CH3OCH2CH2OCH3); 3: Cp′2SmMe2Li(dioxane)} were synthesized from (Cp′2SmCl)2and from the magnesium derivative [Me4C2(C5H4)2]SmCl · MgCl2(THF)4 (4). The ansa anionic complex 2 exhibited good activity for the stereospecific 1,4-trans polymerization of isoprene, whereas the neutral derivative 1 was inactive. In the same way, the anionic complex [Cp′2SmMe2]Li(dioxane) (3) was found to be an ethylene polymerization catalyst of very short lifetime. The lack of reactivity of 1 is related to the associated structure of this coordinatively unsaturated complex: this fact was established by t…

Subphthalocyanines: addressing water-solubility, nano-encapsulation, and activation for optical imaging of B16 melanoma cells

Water-soluble disulfonato-subphthalocyanines (SubPcs) or hydrophobic nano-encapsulated SubPcs are efficient probes for the fluorescence imaging of cells. 20 nm large liposomes (TEM and DLS) incorporated about 13% SubPc. Moreover, some of these fluorophores were found to be pH activatable.

New Porphycene Ligands: Octaethyl- and Etioporphycene(OEPc and EtioPc)—Tetra- and Pentacoordinated Zinc Complexes of OEPc

Titanium imido complexes stabilised by bis(iminophosphoranyl)methanide ligands: the influence of N-substituents on solution dynamics and reactivity

Terminal titanium imido complexes of the general formula [Ti(N(t)Bu)Cl{CH(Ph2PNR)2}] 4 (R = Ph, (i)Pr, (t)Bu) are reported. These compounds were synthesized from the corresponding Li adducts 3 of BIPMH (bis(iminophosphoranyl)methanide) and Mountford's complex [Ti(N(t)Bu)Cl2(Py)3]. The crystal structures of two of the Ti complexes (R = Ph, (t)Bu) and two of the Li compounds (R = (i)Pr, (t)Bu) are reported. Dynamic solution NMR spectroscopy reveals a dynamic isomerisation process in the case of the Ti complex 4c (R = (t)Bu). DFT studies showed that this dynamic process comes from steric repulsion between the imido ligand and the (t)Bu N-substituents on the BIPMH ligand. Complexes 4 were teste…

A P-chirogenic β-aminophosphine synthesis by diastereoselective reaction of the α-metallated PAMP–borane complex with benzaldimine

International audience; The diastereoselective synthesis of a P-chirogenic β-aminophosphine ligand with carbon–carbon bond formation of the ethano bridge in a 3:1 ratio via reaction of an α-metallated P-chirogenic phosphine borane with a benzaldimine is described. The diastereoselectivity is attributed to a transition state where the lithium cation chelates the phosphine borane carbanion and the nitrogen of the imine and the attack of the C@N occurs on the face opposite to the P–B bond, due to its interaction with the antibonding P–B bond. The major diastereoisomeric β-aminophosphine borane was then separated and decomplexed into the corresponding β-aminophosphine under neutral conditions a…

BODIPY atropisomer interconversion, face discrimination, and superstructure appending

International audience; A strategy was developed to append sterically hindered apical pickets on both faces of the BODIPY platform to prevent stacking and aggregation. Ortho-substitution of both the meso-phenyl ring and the boron-bound catechol affords the right directionality to append pickets, achieve face discrimination, featuring two inter-convertible atropisomers, and is reminiscent of the picket-fence strategy in porphyrins.

Design of Porphyrin-dota-Like Scaffolds as All-in-One Multimodal Heterometallic Complexes for Medical Imaging

A series of four multimodal ligands incorporating one porphyrin moiety and one or more dota-like macrocycles all-in-one in the same molecular architecture have been synthesized and full characterized. The corresponding gadolinium(III) complexes were also synthesized and heterometallic complexes incorporating both gadolinium(III) and copper(II) ions were prepared as potential MRI/PET multimodal contrast agents. One ligand (L4) includes an amine moiety that can be activated for easy conversion into an isothiocyanate group for further anchoring to a biological vector. Preliminary relaxivity, cytotoxicity, and MRI studies showed that the complexes developed in this work are very promising medic…

Synthesis and crystal structure of an unprecedented bismuth porphyrin containing ester pendant arms

International audience; An easily prepared porphyrin with pendant arms is shown to form a stable complex with bismuth(III) ion; the complex is eight coordinate with a square antiprismatic coordination geometry; the solid-state structure exhibits the formation of a dimer assembled via mutual coordination of a terminal ester group.

Cyclopentadienylmolybdenum(VI) and molybdenum(V) oxo chemistry: New synthetic and structural features

International audience; Convenient syntheses for Cp, Cp*, and related cyclopentadienyl derivatives (4Cp = C5HiPr4; Cp′′′ = C5H2tBu3-1,2,4) of formula [(Ring)2Mo2O5] are described. Compound [Cp2Mo2O5] was produced in good yields by the rapid oxidation of red [CpMoO2]4 with PhIO in CH2Cl2. [Cp*2Mo2O5] was obtained by CH3COOH acidification of aqueous solutions of [Cp*MoO3]−Na+, the latter being generated in a single step from [Cp*MoCl4] and more than 5 equiv. of aqueous NaOH in air. Minor quantities of [Cp*MoO2]2 were also isolated from this reaction, although the formation of this by-product may be reduced by using a two-step basic hydrolysis procedure. Extension of the latter strategy also a…

[TiPHOS(Rh)]+:  A Fortuitous Coordination Mode and an Effective Hydrosilylation Bimetallic Catalyst

The reaction of the titanocene diphosphine {(η5-C5H5)[η5-C5Me3-1,2-(PPh2)2]TiCl2} (TiPHOS; 1) with [Rh(COD)2](OTf) led to the new early−late heterobimetallic complex [(TiPHOS)Rh(COD)](OTf) (2), who...

1,1′,2,2′-Tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene, a new cisoid arrangement of phosphino groups

Abstract The action of two equivalents of 1,2-bis(diphenylphosphino)-4- tert -butylcyclopentadienyllithium on FeCl 2 led to the corresponding 1,1′,2,2′-tetraphosphinoferrocene. The X-ray structure of this bulky ferrocene is described. The spectroscopic results reveal a conformational chirality with a cisoid disposition of the phosphino groups. The first results about the complexation with representative elements of Group IX and X (Rh, Pd, Ir) are reported.

Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions

A new and facile synthetic route to the known neutral cluster ((PhCH2)2SnO)6[((PhCH2)2SnOH)2- (CO3)]2 (2) as well as its reactivity toward trifluoromethanesulfonic acid (HO3SCF3, TfOH) are reported. The solid-state structure of the new solvate 2·6C7H8 has been determined by single-crystal X-ray diffraction. The core of 2 can be described as a pair of coplanar pentanuclear [(PhCH2)2SnO]5 ladders bridged at their ends by two carbonate groups. Successive additions of TfOH to a suspension of 2 in CD3CN were monitored by 119Sn{1H} NMR spectroscopy showing the transformation of the fingerprint of 2 (δ = −244, −246, −306 ppm), via new upfield signals, to a final broad resonance located at δ = −474…

Dialkyl(butadiene)cyclopentadienylmolybdenum(III) Complexes. Synthesis, Characterization, and Reactivity

International audience; Treatment of CpMo(η4-diene)Cl2 (diene = 1,3-butadiene, C4H6, 1‘; isoprene, C5H8, 1‘ ‘; 2,3-dimethyl-1,3-butadiene, C6H10, 1‘ ‘) in diethyl ether at low temperature with 2 equiv of alkylmagnesium RMgX reagents affords the corresponding dialkyl complexes CpMo(η4-1,3-diene)R2 (2, 2‘, 2‘ ‘, R = CH3, a; CH2Ph, b; CH2SiMe3, c). These species are isolable in moderate yields and have been fully characterized by EPR, elemental analyses, and cyclic voltammetry. They all show a reversible reduction process at relatively low potentials and an irreversible oxidation. The structure of 2‘ ‘a was confirmed by single-crystal X-ray diffraction. The mixed complex CpMo(η4-C4H6)Cl(CH3), …

A reinvestigation of compound CpMo(PMe3)2(CH3)2: Alkylation by single electron transfer and radical addition?

International audience; The synthesis of the half-sandwich molybdenum(III) diphosphine dimethyl complex CpMo(PMe3)2(CH3)2 has been reinvestigated. The compound was obtained from the corresponding dichloro complex CpMo(PMe3)2Cl2 and methyllithium at low temperatures and isolated as a crystalline product by conducting all operations at temperatures lower than −10 °C. The complex is thermally unstable at room temperature but has been fully characterised by EPR spectroscopy, cyclic voltammetry and X-ray diffraction. The formation reaction is retarded by excess phosphine. On the basis of this and other related observations, a mechanism involving phosphine pre-dissociation followed by single elec…

Phosphasalen group IV metal complexes: synthesis, characterization and ring opening polymerization of lactide.

International audience; We report the synthesis of a series of Zr and Ti complexes bearing phosphasalen which differs from salen by the incorporation of two P atoms in the ligand backbone. The reaction of phosphasalen proligands (1a-1c)H2 with Zr(CH2Ph)4 led to different products depending on the nature of the N,N-linker in the ligand. In case of ethylene-linked phosphasalen, octahedral Zr complex 2a formed as a single stereoisomer in trans geometry. With the phenylene linker, it was shown by dynamic NMR spectroscopy that complex 2b exists as a mixture of trans and cis-β isomers in solution, both enantiomers (Δ and Λ) of the cis-β isomer being in fast equilibrium with respect to the NMR tim…

Atom Transfer Radical Addition Catalyzed by Ruthenium–Arene Complexes Bearing a Hybrid Phosphine–Diene Ligand

International audience; The synthesis and characterization of a series of arene ruthenium complexes bearing either (3,5-cycloheptadienyl)diphenylphosphine or (cycloheptyl)-diphenylphosphine are reported. Upon irradiation or heating, all these complexes lose their arene ligand but then exhibit a different behavior depending on the nature of the phosphine ligand. (Cycloheptadienyl)phosphine complexes 1 and 3 give a cationic dinuclear Ru complex 5 for which the two Ru atoms are bridged by three chlorido ligands and flanked by two tridendate (cycloheptadienyl)phosphines. (Cycloheptyl)-diphenylphosphine complexes 2 and 4 undergo arene exchange when toluene is used as solvent or degrade in dithlo…

Phenoxyamidine Zn and Al Complexes: Synthesis, Characterization, and Use in the Ring-Opening Polymerization of Lactide

International audience; Herein we report the synthesis of new ditopic ligands, which consist of a phenoxy group and N,N,N'trisubstituted amidines linked by a methylene spacer (L1-L4). Their coordination chemistry has been studied/investigated with Zn(II) and Al(III). Alkane elimination route between the phenol-amidine proligands (L1H-L4H) and Et2Zn led to dinuclear complexes [(L1-L4)ZnEt]2 (1a-4a) in which the Zn centers are chelated by phenoxyamidine ligands and bridged through the oxygen atom of the phenoxy groups. Salt metathesis reaction between two equivalents of the sodium amidine phenate L1Na and ZnCl2 led to a bis-chelate chiral spiro-complex (L12Zn) 1a'. Analogous alkane eliminatio…

Synthesis and structural studies of TiRu polymetallic systems

Abstract The reaction of the titanocene monophosphines 1 and 2 with the dimer [( p -cymene)RuCl 2 ] 2 give the heterobimetallic compounds ( p -cymene)[(η 5 -C 5 H 4 )(μ-η 5 :η 1 -C 5 H 4 PPh 2 )TiCl 2 ]RuCl 2 and ( p -cymene)[(η 5 -C 5 H 4 )(μ-η 5 :η 1 -C 5 H 4 CH 2 CH 2 PPh 2 )TiCl 2 ]RuCl 2 , respectively. Both structures have been confirmed by X-ray diffraction. By using same procedure, the synthesis of a trimetallic complex RuTiRu has been achieved.

Preparation and structure of the 17-electron (η5-C5R5)Mo(OH)2(dppe) (R=Me, Et) organometallic compounds containing two gem-terminal hydroxide ligands

International audience; Oxidation of (η5-C5R5)MoH3(dppe) (R=Me, Et) by Cp2Fe+ in wet THF leads to the formation of the corresponding (η5-C5R5)Mo(OH)2(dppe). These compounds show a low-potential reversible oxidation wave. The structure of the C5Et5 complex has been confirmed by X-ray diffraction methods: triclinic; space group ; a=11.030(1); b=12.533(1); c=16.241 (1) Å; α=68.585(7); β=75.197(5); γ=83.991(7)°; V=2020.6(3) Å3; Z=2; Dcalc=1.324 g cm−3, μ(Mo–Kα)=0.441 mm−1; R1=0.0325; wR2=0.0875 for 415 parameters and 6823 independent reflections [Rint=0.0177] with I=2σ(I). The molecule shows a four-legged piano-stool geometry with two terminal OH ligands in a relative trans configuration. The c…

Investigation of the Enantioselectivity Observed in Epoxidation Reactions Catalysed by Bis‐Strapped Chiral Porphyrins Derived from L ‐Proline

The enantiomeric excesses obtained during the epoxidation reactions of p-chlorostyrene or 1,2-dihydronaphthalene catalysed by two different series of chiral porphyrins are reported. An attempt is made to correlate the enantioselectivity with the steric hindrance generated by the straps of these catalysts. It is shown that this steric hindrance is influenced by the nature of the strap and that it can be approximated. Additionally, the same strap is tethered in two different fashions on each side of the porphyrin, leading to either D2- or C2-symmetrical catalysts, for which the two sides are identically functionalised.

Assessment of Catalysis by Arene‐Ruthenium Complexes Containing Phosphane or NHC Groups bearing Pendant Conjugated Diene Systems

Two p-cymene-ruthenium complexes 1 and 2 were isolated in high yields by treating the [RuCl2(p-cymene)]2 dimer with new hybrid phosphane- or NHC-linked diene ligands. Both complexes were fully characterized by NMR spectroscopy, and the molecular structure of the ruthenium–p-cymene complex 1, containing the phosphane–diene ligand system, was determined by X-ray diffraction analysis. The catalytic activities of both compounds were probed in atom-transfer radical addition (ATRA) and polymerization (ATRP), in the cyclopropanation of olefins, in the ring-opening metathesis polymerization (ROMP) of norbornene, and in the synthesis of enol esters from hex-1-yne and 4-acetoxybenzoic acid.

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis

Cationic amidotitanocene complexes [Cp2 Ti(NPhAr)][B(C6 F5 )4 ] (Cp=η5 -C5 H5 ; Ar=phenyl (1 a), p-tolyl (1 b), p-anisyl (1 c)) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti-N bond in 1 a-c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a-c undergo photolytic Ti-N cleavage to release Ti(III) species and aminyl radicals ⋅NPhAr. Reaction of 1 b with H3 BNHMe2 results in fast homolytic Ti-N cleavage to give [Cp2 Ti(H3 BNHMe2 )…

Self-assembly through non-coordinating intermolecular forces, part 2 [1]. Synthesis, crystal structure and packing of [Cu2(μ-phthalazine) 3(phthalazine)2][CF3SO3]2

Abstract Treatment of the copper(I) trifluoromethanesulphonate toluene complex {[Cu(CF3SO3)]2 · C6H5Me} (1) with phthalazine (phtz, C8H6N2) in dichloromethane-acetonitrile solution yielded, via the bis(acetonitrile)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate intermediate (2), the novel bis(phthalazine)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate salt (3). Compound 3 was completely characterised and the molecular structure determined by single-crystal X-ray diffraction. Complex 3 crystallises in the monoclinic system, space group C2/c, with a = 26.9527(10), b = 10.9558(7), c = 19.2104(10) Å , β = 127.268(2)◦, V = 4514.3(4) Å3 and Z = 4. The copper(I) coordination g…

A Versatile and Convenient Method for the Functionalization of Porphyrins

International audience; The condensation of 3-(chloromethyl)benzoyl chloride with different atropisomers of meso-(tetra-o-aminophenyl)porphyrin (TAPP), followed by the reaction of a series of nucleophilic reagents leads, among others, to precursors of biomimetic models of heme proteins such as cytochrome c oxidase (CcO). This synthesis can also be applied as an efficient two-step reaction to obtain highly functionalized porphyrin derivatives potentially useful for cation binding.

How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation using organometallic MoIII-based catalysts

International audience; Compound CpMoI2(iPr2dad) (iPr2dad = iPrNdouble bondCHsingle bondCHdouble bondNiPr), obtained by halide exchange from CpMoCl2(iPr2dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl2(iPr2dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irre…

ChemInform Abstract: nBuLi-Mediated Hydrophosphination: A Simple Route to Valuable Organophosphorus Compounds.

A straightforward synthesis of homoallyl- and allylphosphanes has been developed using nBuLi-mediated hydrophosphination of conjugated dienes. In all the cases the phosphorus atom of the reacting phosphane attacked the sterically less demanding side of the diene exclusively. In addition, high regioselectivities towards 1,2- or 1,4-addition products were observed depending on the nature of the dienes. This hydrophosphination reaction was extended to a variety of substrates such as styrene derivatives, alkynes and 1,3,5-cycloheptatriene. The structures of three hydrophosphination products were confirmed by X-ray diffraction studies.

Coupling of Benzynezirconocene with 1,4-Diphenyl-1,3-butadiyne

The thermolysis of diphenylzirconocene in the presence of 1,4-diphenyl-1,3-butadiyne to yield the seven-membered zirconacyclocumulene 1 via the intermediacy of benzynezirconocene is described. This complex has been characterized by an X-ray diffraction study. Additionally, better knowledge of the bonding of the cumulene moiety was achieved by DFT calculations. Cleavage of the Zr−C bonds of 1 with methanol provided the corresponding butatriene 2.

Rh(I) Coordination Chemistry of Chiral α-Aminophosphine(η6-arene)chromium Tricarbonyl Ligands

The diastereoselective addition of Ph(2)PH to the chiral ortho-substituted eta(6)-benzaldimine complexes (eta(6)-o-X-C(6)H(4)CH=NAr)Cr(CO)(3) (1, X = MeO, Ar = p-C(6)H(4)OMe; 2, X = Cl, Ar = Ph) leads to the formation of the corresponding chiral aminophosphines (alpha-P,N) Ph(2)P-CH(Ar(1))-NHAr(2) (3, Ar(1) = o-C(6)H(4)(OCH(3))[Cr(CO)(3)], Ar(2) = p-C(6)H(4)OCH(3); 4, Ar(1) = o-C(6)H(4)Cl[Cr(CO)(3)], Ar(2) = Ph) in equilibrium with the starting materials. The uncomplexed benzaldimine (o-ClC(6)H(4)CH=NPh), 2', analogously produces an equilibrium amount of the corresponding aminophosphine Ph(2)P-CH(Ar(1))-NHAr(2) (4', Ar(1) = o-C(6)H(4)Cl, Ar(2) = Ph). Depending on the equilibrium constant, t…

Electrochemistry and Spectroelectrochemistry of Bismanganese Porphyrin-Corrole Dyads

A series of homobimetallic manganese cofacial porphyrin-corrole dyads were synthesized and investigated as to their electrochemistry, spectroelectrochemistry, and ligand binding properties in nonaqueous media. Four dyads were investigated, each of which contained a Mn(III) corrole linked in a face-to-face arrangement with a Mn(III) porphyrin. The main difference between compounds in the series is the type of spacer, 9,9-dimethylxanthene, anthracene, dibenzofuran, or diphenylether, which determines the distance and interaction between the metallomacrocycles. Each redox process of the porphyrin-corrole dyads was assigned on the basis of spectroscopic and electrochemical data and by comparison…

New chiral α-aminophosphine oxides and sulfides: an unprecedented rhodium-catalyzed ligand epimerization

International audience; New chiral α-aminophosphine oxide N,P(O) and sulfide N,P(S) ligands have been prepared in one-pot syntheses by addition of Ph2PH to (S)-PhCH[double bond, length half m-dash]NCH(Ph)CH3, followed by oxidation with O2 or S8. Crystallization from cold methanol leads to the isolation of an enantiomerically pure single N,P(O) diastereomer and to a 1 : 1 mixture of the two N,P(S) diastereomers. The coordination chemistry of these ligands with [RhCl(COD)]2 and [RhCl(CO)2]2 has been investigated under argon and syngas. At high temperatures, a P–C oxidative addition of the N,P(O) ligand followed by imine elimination leads to several hydrido rhodium species. The complexes conta…

Multinuclear Cytotoxic Metallodrugs: Physicochemical Characterization and Biological Properties of Novel Heteronuclear Gold-Titanium Complexes

An unprecedented series of titanocene-gold bi- and trimetallic complexes of the general formula [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)](m)AuCl(x)](q+) (n = 0, 2, or 4; m = 1, x = 1, q = 0 or m = 2, x = 0, q = 1) have been prepared and characterized spectroscopically. The luminescence spectroscopy and photophysics of one of the compounds, [[(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)PPh(2))TiCl(2)](2)Au]PF(6), have been investigated in 2MeTHF solution and in the solid state at 77 and 298 K. Evidence for interfragment interactions based on the comparison of electronic band positions and emission lifetimes, namely, triplet energy transfer (ET) from the Au- to the Ti-containing…

Ruthenium titanocene and ruthenium titanium half-sandwich bimetallic complexes in catalytic cyclopropanation

Abstract The reaction of the phosphine functionalised titanium half-sandwich complexes 7, 9 and 10 with the binuclear complex [(p-cymene)RuCl2]2 allowed the access to three new early-late bimetallic complexes (p-cymene)[(μ-η5:η1-C5H4(CH2)nPR2)TiX3]RuCl2 (11–13). The structure of 11 (n = 0, X = Cl) has been confirmed by X-ray diffraction. The ruthenium titanium half-sandwich bimetallic complexes so formed and the ruthenium titanocene analogues 4–6 catalyse the addition of ethyl diazoacetate to styrene with high selectivity toward cyclopropanation versus metathesis contrary to the monometallic complexes (p-cymene)RuCl2PR3.

Hexaphosphine: A Multifaceted Ligand for Transition Metal Coordination

We report the synthesis and characterization of the first ferrocenyl polyphosphane incorporating six phosphorus donor atoms. In this unique ligand, the cyclopentadienyl rings of the ferrocenyl backbone adopt a staggered position, which leads to a piano-stool arrangement for each of the two sets of three P atoms facing the same direction. As a consequence of its remarkable flexibility, this hexaphosphane displays versatile coordination behaviour towards metals, leading to unexpected structures of palladium and platinum bimetallic complexes. Analogous molybdenum and rhodium complexes are more classical.

Synthesis of new half sandwich tetrachloro derivatives of molybdenum(V) and tungsten(V). X-ray structures of (C5HPri4)W(CO)3(CH3) and (C5Et5)WCl4

International audience; The new synthetic intermediates (Ring)MCl4 [Ring=C5HPri4 or 4Cp, M=Mo, 2; Ring=C5Et5 or VCp, M=W, 4, Ring=4Cp, M=W, 6] containing sterically protecting cyclopentadienyl ligands have been synthesized. Along the synthetic pathway to 2, it was found that the treatment of [4CpMo(CO)3]− with an aqueous ferric solution according to the well established Manning procedure affords the hydride compound 4CpMo(CO)3H (1) by hydrolysis rather than the expected neutral dimer by oxidation. Compound 1 could be converted, however, to 2 upon oxidation with PhICl2 in good yields. Compound 4 is shown by a single crystal X-ray analysis to adopt a monomeric four-legged piano stool structur…

Addressing subphthalocyanines and subnaphthalocyanines features relevant to fluorescence imaging

International audience; A series of new synthetic subphthalocyanines bear structural features aimed at allowing either fluorescence activation or a bathochromic shift of the absorption band towards the near-infrared window, relevant to optical imaging. X-ray diffraction studies of four subphthalocyanines are reported. Spectrofluorimetric studies on subnaphthalocyanines and activatable subphthalocyanine pro-fluorophores are reported.

A Route toward (Aminomethyl)cyclopentadienide Ligands and Their Group 4 Metal Complexes

International audience

Shape-persistent poly-porphyrins assembled by a central truxene: synthesis, structure, and singlet energy transfer behaviors

Four dyad systems composed of a central truxene and either one or three β-substituted zinc(II) porphyrins (ZnP: TruZnP (7) and TruTriZnP (9)) or free-bases (H2P: TruP (6) and TruTriP (8)) have been prepared. The presence of β-methyl groups minimizes π-conjugation through the quasi right angle made by the porphyrin and the truxene planes, and renders these dyads relatively rigid. The position of the absorption and emission 0–0 peaks confirms the role of the truxene and porphyrin as the energy donor and acceptor, respectively. Selective excitation of the truxene results in an efficient singlet energy transfer (S1 ET) from the truxene to the porphyrin unit. The rates for S1 ET (k ET ) are ext…

Enantiodivergent synthesis of P-chirogenic phosphines

International audience; Several approaches for the enantiodivergent synthesis of P-chirogenic mono- and diphosphines are described, using ephedrine methodology and phosphine borane chemistry. Firstly, both enantiomers of a tertiary phosphine can be obtained starting from the same oxazaphospholidine borane complex, prepared from (+)-ephedrine, when changing the order of addition of the organolithium reagents during the synthetic pathway. The second approach is based on the chlorophosphine boranes, which react with an organolithium reagent, to afford the corresponding phosphines with inversion of configuration. In the case where the chlorophosphine borane reacts with the t-butyl lithium reage…

Di-n-butyltin oxide as a chemical carbon dioxide capturer

Abstract Several synthetic routes to the decakis(di-n-butyltin(IV)) oxocluster, (n-Bu2SnO)6[(n-Bu2SnOCH3)2(CO3)]2 (1), a diorganotin compound previously shown to belong to the class of organotins able to store carbon dioxide, as well as its reactivity toward dimethyl carbonate (DMC), are described. The synthetic route from n-Bu2SnO and DMC was applied for the preparation of the ethoxy analogue of 1, oxocluster 2, using diethyl carbonate. The structural relationship connecting cluster 1, with its precursor PRE-1 isolated from recycling experiments and n-Bu2SnO is discussed. For this purpose, the reactivity of PRE-1 with trifluoromethanesulfonic acid was investigated in order to trace structu…

Half-sandwich molybdenum(III) compounds containing diazadiene ligands and their use in the controlled radical polymerization of styrene

Abstract The reaction of CpMoCl2 with diazadiene ligands RNCHCHNR (R2dad) affords the corresponding paramagnetic complexes CpMoCl2(R2dad) (R=Ph, 1; p-Tol, 2; C6H3Pr2i-2,6, 3; and Pri, 4). All compounds have been characterized by EPR spectroscopy and have been investigated by cyclic voltammetry. They display one-electron oxidation and reduction processes, these being reversible or irreversible depending on the nature of R. The irreversibility of the reduction wave is due to a chemical follow-up process which consists of chloride loss from the reduced product. This phenomenon is suppressed in the presence of excess chloride in solution. An X-ray structure of 3 verifies the mononuclear na…

Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]

Abstract The reactions of the half-sandwich molybdenum(III) complexes CpMo(η 4 -C 4 H 4 R 2 )(CH 3 ) 2 , where Cpη 5 -C 5 H 5 and RH or CH 3 , with equimolar amounts of B(C 6 F 5 ) 3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe 3 . The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η 4 -C 4 H 6 )(μ-Cl)(μ-CH 2 )(O)MoCp][CH 3 B(C 6 F 5 ) 3 ], indicate that the borane attack has occurred at the methyl position.

Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate

The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with din-butyldimethoxystannane in order to get insight into the reaction mechanism for activity improvement. Catalytic runs including recycling experiments allowed isolation and characterization by NMR, IR, and single-crystal X-ray diffraction of a new tin complex containing 10 tin atoms. This compound could be prepared independently and is considered as a resting species. The yield of DMC is highest under 20 MPa pressure that fits with a monophasic supercritical medium in agreement with fluid phase equilibria calculations. In line, preliminary kinetics and…

First donor stabilized-phosphenium rhodium complexes

Abstract The coordination properties of a donor stabilized-phosphenium adduct have been examined in rhodium chemistry. The preparation as well as the characterization of the first examples of donor stabilized-phosphenium rhodium(I) complexes is reported in this paper. Indeed, mono- and di-cationic rhodium complexes were obtained in quantitative yield by the direct addition of this imidazolium P(III)-ligand to [RhCl(1,5-COD)] 2 in CH 2 Cl 2 solution with a 1:1 P/Rh ratio under argon and 2:1 P/Rh ratio under CO atmosphere, respectively. Crystal structure of the bis-cationic donor stabilized-phosphenium rhodium(I) complex has been obtained from an acetone/pentane mixture. Its molecular structu…

ChemInform Abstract: A Straightforward Route to Homoallyl-Homocrotylamines Promoted by a Titanium Complex.

This publication also contains theoretical studies and calculations concerning the reaction.

A Two-State Computational Investigation of Methane C-H and Ethane C-C Oxidative Addition to [CpM(PH3)]n+ (M=Co, Rh, Ir;n=0, 1)

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordinati…

Coumarin-Phosphine-Based Smart Probes for Tracking Biologically Relevant Metal Complexes: From Theoretical to Biological Investigations

International audience; Ten metal-based complexes and associated ligands have been synthesized and characterized. One of the metal ligands is a coumarin-phosphine derivative, which displays tunable fluorescence properties. The fluorescence is quenched in the case of the free ligand and ruthenium and osmium complexes, whereas it is strong for the gold complexes and phosphonium derivatives. These trends were rationalized by theoretical calculations, which revealed non-radiative channels involving a dark state for the free ligands that is lower in energy than the emissive state and is responsible for the quenching of fluorescence. For the Ru-II and Os-II complexes, other non-radiative channels…

Design of guanidinium porphyrins as potential G-quadruplex ligands

We report herein an easy and smooth synthesis of two novel tetra-meso-substituted porphyrins bearing terminal guanidinium functionalities. These two guanidine derivatives are the porphyrin-based analogs of ZnPC , a closely related phthalocyanine-based molecule with four guanidinium arms already reported as an efficient G-quadruplex ligand.

Towards a Library of “Early‐Late” Ti–Ru Bimetallic Complexes

A series of new titanocene phosphanes 3–6 have been prepared by replacing both chloride atoms at the titanium atom of the complexes [TiCl2(η5-C5H5){η5-C5H4(CH2)2PR2}] (1: R = Ph; 2: R = Cy) by sodium fluoride or sodium benzoate in two-phase systems. Treatment of these new metalloligands with the binuclear complex [(p-cymene)RuCl2]2 affords the targeted titanocene difluoride and titanocene dibenzoate bimetallic ruthenium complexes 8–11. The first chiral Ti–Ru bimetallic complex 12 bearing a binaphthyloxy ligand at the titanium centre has been synthesised in this way. In each series, an X-ray crystal structure has been determined. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, …

Synthetic Endeavors toward Titanium Based Frustrated Lewis Pairs with Controlled Electronic and Steric Properties

A new family of cationic Ti complexes 4′ with a pendant phosphine of general formula [CpCpPTiOAr][BPh4] (Cp = η5-C5H5; CpP = η5-C5H4(CMe2)PR2) has been prepared in four steps from 6,6-dimethylfulvene. These complexes were designed to behave as Ti based frustrated Lewis pairs (FLPs). The key synthetic step is a reduction–oxidation sequence from [CpCpPTiClOAr] complexes 3 using lithium phosphide salts as the reductants and ferricinium tetraphenylborate as the oxidant. Four complexes have been structurally characterized by X-ray diffraction and show elongated Ti–P bonds, above 2.60 A. One complex (4b′: OAr = 2,6-Me2C6H3; PR2 = PCy2) reacted with benzaldehyde to form a typical FLP activation pr…

Catena-poly[[di-n-butyltin(IV)]-mu-trifluoromethanesulfonato-[[di-n-butyl(trifluoromethanesulfonato)tin(IV)]-di-mu-hydroxo]]

International audience

Half-sandwich complexes of molybdenum-(III), -(IV) and -(V) with P–O and P–N bifunctional ligands Ph2PCH2X (X = 2-oxazolinyl, or C(O)NPh2)

International audience; The reaction of the ligands Ph2PCH2X (X = 2-oxazolinyl, I; or C(O)NPh2, II) with the half-sandwich molybdenum(III) precursors [Mo(η-C5R5)(μ-Cl)2]2 (R = H or Me) has been investigated. Ligand I reacts with both complexes to form the corresponding adducts [Mo(η-C5R5)Cl2(Ph2PCH2C3H4NO)] (R = H, 1; or Me, 2). The reaction between I and [MoCp*Cl4] (Cp* = η-C5Me5) affords [MoCp*Cl4(Ph2PCH2C3H4NO-κ1P)] as a kinetic isomer, which then transforms quantitatively to [MoCp*Cl3(Ph2PCH2C3H4NO-κ2P,N)]+Cl−, 3. Ligand II reacts with [MoCp(μ-Cl)2]2 (Cp = η-C5H5) to afford the adduct [CpMoCl2{Ph2PCH2C(O)NPh2-κ2P,O}], 4, as an equilibrium mixture of two isomers. Longer reaction times in…

The synthesis and X-ray study of (η6-benzamide)- and (η6-phenylacetamide)tricarbonyl chromium complexes. Structural effects of the substituent

(η6-Benzamide)tricarbonylchromium and tricarbonyl(η6-phenylacetamide)chromium (1 and 2) have been synthesized from the corresponding amides and chromium hexacarbonyl. Decalin, a mixture of decalin and butyl acetate, and neat butyl acetate have been used as the reaction media. The first system gave best yields. Both amide complexes form adducts with non-complexed molecules of the type [(CO3)CrL] · L through hydrogen bonds, suggested on the basis of 1H and 13C NMR spectroscopy. Similar associations by hydrogen bonds exist in the solid state structure of 3 and 4. The π-donor-acceptor abilities of the substituents on the rings are discussed on the basis of geometrical parameters and 13C NMR dat…

The Taming of Redox‐Labile Phosphidotitanocene Cations

International audience; Tame d0 phosphidotitanocene cations stabilized with a pendant tertiary phosphane arm are reported. These compounds were obtained by one-electron oxidation of d1 precursors with [Cp2Fe][BPh4]. The electronic structure of these compounds was studied experimentally (EPR, UV/Vis, and NMR spectroscopy, X-ray diffraction analysis) and through DFT calculations. The theoretical analysis of the bonding situation by using the electron localization function (ELF) shows the presence of π-interactions between the phosphido ligand and Ti in the d0 complexes, whereas dπ–pπ repulsion prevents such interactions in the d1 complexes. In addition, CH–π interactions were observed in seve…

High oxidation state aqueous organometallics. Formation and structure of an oxo-centred Cp*MoV trinuclear cation by chemical reduction of Cp*2Mo2O5

International audience; Reduction of Cp*2Mo2O5 by zinc/CF3CO2H in MeOH–H2O yields a salt which is composed of [Cp*3Mo3O4(O2CCF3)3]+ and [Zn2(O2CCF3)6]2− ions after crystallisation from THF–Et2O.

Porphyrin-Based Design of Bioinspired Multitarget Quadruplex Ligands

Secondary nucleic acid structures, such as DNA and RNA quadruplexes, are potential targets for cancer therapies. Ligands that interact with these targets could thus find application as anticancer agents. Synthetic G-quartets have recently found numerous applications, including use as bioinspired G-quadruplex ligands. Herein, the design, synthesis and preliminary biophysical evaluation of a new prototype multitarget G-quadruplex ligand, (PNA)PorphySQ, are reported, where peptidic nucleic acid guanine ((PNA)G) was incorporated in the porphyrin-templated synthetic G-quartet (PorphySQ). Using fluorescence resonance energy transfer (FRET)-melting experiments, PorphySQ was shown to possess enhanc…

Synthesis and Spectral and Structural Characterization of a New Series of Bis-Strapped Chiral Porphyrins Derived from L-Proline

International audience; New chiral porphyrins were obtained in reasonable yields in three steps, starting from the áâáâ atropisomer of mesotetrakis(o-aminophenyl)porphyrin (TAPP). These potential catalysts for the enantioselective epoxidation of alkenes were obtained by the reaction of different linkers on the same Lprolinoyl-picket porphyrin. Their 1H NMR spectral characteristics, as well as the crystal structure of one of them, clearly indicate that the orientation of the proline cycle depends on the linker used to tether the two pickets on each side of the porphyrin. The same linker is employed for both sides of the porphyrin; hence the resulting D2-symmetric superstructure.

Assessing the Differential Affinity of Small Molecules for Noncanonical DNA Structures

The targeting of higher-order DNA structures has been thoroughly developed with G-quadruplex DNA but not with other structures like branched DNA (also known as DNA junctions). Because these alternative higher-order DNA architectures might be of high biological relevance, we implemented a high-throughput version of the FRET melting assay that enabled us to map the interactions of a candidate with four different DNA structures (duplex- and quadruplex DNA, three- and four-way junctions) in a rapid and reliable manner. We also introduce a novel index, the BONDS (branched and other noncanonical DNA selectivity) index, to conveniently quantify this differential affinity.

Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fragment

International audience; A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis-(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis-(5-methy1-2-furyl)phosphino]-3,3'-di-tert-butyfferrocene (5-r), and rac-1,1'-bis ( diphenylphos…

A novel two-dimensional organostannoxane coordination network promoted by phenazine: Synthesis, characterization and X-ray structure of

Abstract Reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(μ-OH)(H2O)0.5(η1-O3SCF3)]2 (1) with phenazine (C12H8N2, Phz) (2) in dichloromethane at room temperature in a 1:3 molar ratio yielded the novel two-dimensional organometallic coordination polymer 2 ∞ { [ n - Bu 2 ( μ -OH ) SnOSn ( μ - η 2 - O 3 SCF 3 ) n - Bu 2 ] 2 [ n - Bu 2 ( μ -OH ) SnOSn ( η 1 - O 3 SCF 3 ) n - Bu 2 ] 2 } (3), together with the phenazinium trifluoromethanesulfonate salt [C12H9N2]+ [CF3SO3]−, crystallographically isolated in two different structural arrangements, free 4 and in π–π aromatic stacking interaction with independent intercalated non-protonated phenazine molecu…

Allylpalladium( II ) Complexes with Aminophosphane Ligands: Solution Behaviour and X‐ray Structure of cis ‐[Pd(η 3 ‐CH 2 CHCHPh){Ph 2 PCH 2 CHPhNH(2,6‐C 6 H 3 i Pr 2 )}][PF 6 ]

A new β-aminophosphane L2 [Ph2PCH2CH(Ph)NH(2,6-C6H3iPr2)], bearing an asymmetric carbon atom and a vicinal prochiral nitrogen centre and (η3-allyl)palladium complexes of general formula [Pd(η3-C3H4R){η2-Ph2PCH2CH(Ph)NHAr}][PF6] (1−6) (R = H, Me or Ph and Ar = Ph or 2,6-C6H3iPr2) have been synthesised. NMR spectroscopic studies and a crystal structure analysis of complex 6 (R = Ph, Ar = 2,6-C6H3iPr2) confirmed the highly diastereoselective coordination of the nitrogen atom. Because of the allyl fluxionality and the presence of asymmetric centres, all the complexes exist in solution as mixtures of up to four diastereomers. For the monosubstituted allyl complexes [Pd(η3-C3H4R){Ph2PCH2CH(Ph)NHA…

Straightforward synthesis of donor-stabilised phosphenium adducts from imidazolium-2-carboxylate and their electronic properties

Cationic imidazolium-2-phosphanes were obtained by the addition of a chlorophosphane (R2PCl, R = Ph, iPr or Cy) to 1,3-dimethylimidazolium-2-carboxylate without the need for a purification step. An additional anion exchange reaction with KPF6 led to the corresponding halide-free ligands in excellent yields. The molecular structure of one of them was examined both in the solid state and in solution. The lone pair of electrons on the phosphorus atom is not delocalised to the imidazolium fragment and thus remains available for further metal coordination. As such compounds can be described as phosphenium cations stabilised by a N-heterocarbene donor base, the electronic properties of the Lewis …

nBuLi-Mediated hydrophosphination: a simple route to valuable organophosphorus compounds

A straightforward synthesis of homoallyl- and allylphosphanes has been developed using nBuLi-mediated hydrophosphination of conjugated dienes. In all the cases the phosphorus atom of the reacting phosphane attacked the sterically less demanding side of the diene exclusively. In addition, high regioselectivities towards 1,2- or 1,4-addition products were observed depending on the nature of the dienes. This hydrophosphination reaction was extended to a variety of substrates such as styrene derivatives, alkynes and 1,3,5-cycloheptatriene. The structures of three hydrophosphination products were confirmed by X-ray diffraction studies.

Half-sandwich Mo(III) complexes with asymmetric diazadiene ligands

The asymmetric 1,4-diazadiene ligands R ∗ N CHCH NR ∗ [R ∗  = ( S )-CH(CH 3 )Ph], R 2 ∗ dad , and 2,2′-bis(4-ethyloxazoline), as-ox, have been used to generate half-sandwich Mo III derivatives by addition to Cp 2 Mo 2 Cl 4 . Ligand R 2 ∗ dad affords a mononuclear, paramagnetic 17-electron product, CpMoCl 2 ( R 2 ∗ dad ) , whereas as-ox leads to the isolation of a dinuclear compound where only one molecule of ligand has been added per two Mo atoms, Cp 2 Mo 2 Cl 4 (as-ox). In the presence of free as-ox, this compound coexists with the paramagnetic mononuclear complex in solution. Both products are capable of controlling the radical polymerization of styrene under typical atom transfer radical…

Selective formation of a unique diphosphonium-diphosphine from a tetraphosphine double protonation induced by zirconium salts

A mixed ferrocenyl diphosphonium-diphosphine cation, associated with two [ZrCl(5).thf](-) anions, is obtained from a ferrocenyl tetraphosphine, as a unique didentate ionic metalloligand in a perfectly selective reaction induced by ZrCl(4) in THF.

Functionalization of Porphyrins: Mechanistic Insights, Conformational Studies, and Structural Characterizations

The condensation of 3-chloromethylbenzoyl chloride with three atropisomers of meso-5,10,15,20-tetrakis(2-aminophenyl)porphyrin (TAPP) is reported, followed by the reaction of the anion of diethyl malonate to prepare various strapped porphyrins. According to two different geometries of the straps, the resulting preorganization of the hanging ethoxycarbonyl groups is more or less adapted to the coordination of cations such as lanthanides. The conformational study, as well as the X-ray structures of three strapped porphyrins, demonstrate that among the three atropisomers investigated in this work, only two of them lead to strapped porphyrins in which an ethoxycarbonyl group is directed towards…

Ruthenium and Osmium Complexes of Phosphine-Porphyrin Derivatives as Potential Bimetallic Theranostics: Photophysical Studies

A series of (η6-p-cymene)ruthenium(II)- and osmium(II) complexes of porphyrin-phosphane derivatives have been synthesized as potential bimetallic theranostic candidates. The photophysical and electrochemical properties were investigated, and these species desirably exhibit no or almost no photoinduced intramolecular atom, energy, and electron transfer between the dye and the metallic fragment. These favorable features are mostly associated with the presence of their long chain (i.e., ∼ 1 nm) separating the two functional units. Interestingly, a decrease in emission intensity and lifetimes (up to 35-fold) has been observed, which was ascribed to a small heavy atom effect. This effect is poss…

Synthesis, characterisation, and molecular and electronic structure of CpMoCl2(R1C≡CR2) (R1, R2 = Ph, Et, Me): a new class of half-sandwich 17-electron molybdenum(III) organometallics

International audience; Addition of alkyne to [CpMoCl2]2 affords compounds CpMoCl2(η2-alkyne) (alkyne = EtC[triple bond, length as m-dash]CMe, 1; EtC[triple bond, length as m-dash]CEt, 2; PhC[triple bond, length as m-dash]CMe, 3; PhC[triple bond, length as m-dash]CPh, 4) in good yields. The compounds have been characterised by C,H analyses, IR, EPR and mass spectroscopies, magnetic susceptibility, and cyclic voltammetry. In addition, a single crystal X-ray diffraction analysis has been carried out for compound 4. The alkyne ligand adopts an almost parallel conformation relative to the Cp ring, essentially identical with that of previously reported Nb, Ta, and W analogues. Geometry optimisat…

Porphyrin-templated synthetic G-quartet (PorphySQ): a second prototype of G-quartet-based G-quadruplex ligand.

Template-assembled synthetic G-quartet (TASQ) has been reported recently as a G-quadruplex ligand interacting with DNA according to an unprecedented, nature-inspired ‘like likes like’ approach, based on the association between two G-quartets, one being native (quadruplex) and the other one artificial (ligand). Herein, a novel TASQ-based ligand is designed, synthesized and its quadruplex-recognition properties are evaluated in vitro: PorphySQ (for porphyrin-templated synthetic G-quartet) displays enhanced quadruplex recognition properties as compared to the very first reported prototype (DOTASQ, for DOTA-templated synthetic G-quartet), since the porphyrin template insures a more stable intra…

(Cycloheptadienyl)diphenylphosphine: A Versatile Hybrid Ligand

(3,5-Cycloheptadienyl)diphenylphosphine is easily synthesized from the reaction of diphenylphosphine with 1,3,5-cycloheptatriene. This new phosphine-diene has been coordinated as a monodentate P ligand with Pt, Pd, Au, Ni, and Ru; as a bidentate (P, olefin) ligand with Pt and Pd; and as a tridentate (P, diene) ligand with Rh. Fluxional properties of several complexes have been studied via NMR experiments and theoretical consideration.

Synthesis and structure of a new organometallic polyoxomolybdate,

Abstract Acidic aqueous solutions of the [Cp*MoO2(H2O)x]+ ion yield single crystals of the novel organometallic polyoxomolybdate Cp 2 ∗ Mo 6 O 17 via a slow protonolysis of the Mo–Cp* bond. This compound has subsequently been obtained selectively and in good yields from the combination of Cp 2 ∗ Mo 2 O 5 and four equivalents of MoO 4 2 - under acidic conditions. The X-ray structure of Cp 2 ∗ Mo 6 O 17 is analogous to other hexanuclear polyoxometallate ions but is the most distorted so far reported according to the continuous symmetry measure, the inner (μ6-O)Mo6 core featuring a large displacement of the central oxygen atom toward the organometallic moieties and away from the inorganic ones.

{1,1′-Bis[bis(5-methyl-2-furyl)phosphino]ferrocene-κ2P,P′}dichloroplatinum(II) dichloromethane hemisolvate

The synthesis of the title compound, [FePtCl2(C15H14O2P)2]·0.5CH2Cl2, has been achieved by reacting PtCl2(PhCN)2 with the 1,1′-bis­[bis­(5-methyl-2-furyl)phosphino]ferrocene chelating ligand. The environment at the Pt atom can be described as distorted square-planar, with two cis-Cl atoms and two cis-P atoms.

Three-Metal Coordination by Novel Bisporphyrin Architectures

The synthesis and characterization of a new type of bisporphyrin system is reported where the two macrocycles are linked in a cofacial arrangement by a substituted carbazole bridge. The three nitrogen atoms of the carbazole bridge in the compounds may complex a metal ion and thus provide a new parameter for varying the physical properties and flexibility of the dyad after formation of a three-metal system. In the present study, four bis-metalloporphyrin complexes were synthesized and examined by electrochemistry and thin-layer spectroelectrochemistry in CH(2)Cl(2) and PhCN. Two of the examined compounds contain Cu(II) or Zn(II) porphyrins and a carbazole linker with a bound Cu(II) ion, givi…

Structural characterization of 2,2-di-n-butyl-4-methyl-1,3,2-dioxastannolane isolated from supercritical CO2 conditions

The title compound has been isolated as single crystals from the synthesis of propylene carbonate from racemic 1,2-propanediol and carbon dioxide using n-Bu2SnO as a catalyst precursor. The X-ray crystallographic structure analysis revealed the self-assembly of di-n-butyltin(IV) 1,2-propanediolate units, linked together through long-distance Sn-O interactions leading to a one-dimensional polymeric architecture organized in a syndiotactic arrangement. The coordination geometry around the tin atoms can be described as an unusual faced-capped trigonal bipyramidal environment.

Cover Feature: A Route toward (Aminomethyl)cyclopentadienide Ligands and Their Group 4 Metal Complexes (Eur. J. Inorg. Chem. 34/2018)

ChemInform Abstract: New Porphycene Ligands: Octaethyl- and Etioporphycene (OEPc and EtioPc) - Tetra- and Pentacoordinated Zinc Complexes of OEPc.

Development of Bimetallic Titanocene−Ruthenium−Arene Complexes As Anticancer Agents: Relationships between Structural and Biological Properties

A series of bimetallic titanium-ruthenium complexes of general formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CR(2))(n)PR'R'')TiCl(2)](η(6)-p-cymene)RuCl(2) (n = 0, 1, 2 or 4; R = H or Me; R' = H, Ph, or Cy; R'' = Ph or Cy) have been synthesized, including two novel compounds as well as two cationic derivatives of formula [(η(5)-C(5)H(5))(μ-η(5):κ(1)-C(5)H(4)(CH(2))(n)PPh(2))TiCl(2)] [(η(6)-p-cymene)RuCl](BF(4)) (n = 0 or 2). The solid state structure of two of these compounds was also established by X-ray crystallography. The complexes showed a cytotoxic effect on human ovarian cancer cells and were markedly more active than their Ti or Ru monometallic analogues titanocene dichloride and RA…

Iron Porphyrins as Models of Cytochromec Oxidase

A series of iron porphyrins has been synthesized as models of cytochrome c oxidase; their activity as 4 e− catalysts in the reduction of dioxygen has been studied at pH 7. These compounds have been obtained by grafting very different residues onto the same iron complex, namely tripodal tetraamines, pickets, and straps, in order to change the environment of the metal center. In the case of porphyrins bearing a tripodal cap, the secondary amines have been alkylated with different substituents so as to modify the electronic environment of the distal pocket. Surprisingly, when the iron porphyrin is functionalized with four identical acrylamido pickets, the resulting complex exhibits biomimetic …

The ionic tin(IV) complex tri-μ2-methoxy-μ3-oxo-tris[di-tert-butyltin(IV)] tri-μ2-methoxy-bis[tert-butyldimethoxystannate(IV)]

The solid-state of the title compound, [Sn3(C4H9)6(CH3O)3O][Sn2(C4H9)2(CH3O)7], consists of distinct [tBu6Sn3(μ-OCH3)3(μ3-O)]+ cations and [tBu2Sn2(OCH3)4(μ-OCH3)3]− anions, apparently formed as a result of slow hydro­lysis of pure di(tert-butyl)­di­methoxy­stannane, tBu2Sn(OCH3)2. In the monocation, the coordin­ation about the Sn atoms is distorted trigonal bipyramidal, and, in the monoanion, distorted octahedral. The trigonal bipyramidal arrangement induces planarity of the Sn3O4 motif.

Mixed Titanium–Hafnium Chloridometallate Complexes

The addition of either NEt 3 BzCl or [Ph 3 PNPPh 3 ]Cl (1 equiv. chloride per metal) to a 1:1 mixture of HfCl 4 and TiCl 3 in SOCl 2 results in Ti oxidation and leads to the corresponding salts of the [TiHfCl 10 ] 2- ion. A solution IR investigation in the v(M-Cl) region indicates that this ion is in equilibrium with the homodimetallic [Ti 2 Cl 10 ] 2- and [Hf 2 Cl 10 ] 2- ions. An X-ray study of the NEt 3 Bz + salt reveals an edge-sharing bioctahedral dianion sitting on a crystallographic inversion centre. The crystal is a solid solution of different species with compositional disorder at the metal site, each metal position having the occupancy Ti 0.685 Hf 0.315 . The M-M and M-Cl distance…

First copper(I) ferrocenyltetraphosphine complexes: possible involvement in Sonogashira cross-coupling reaction ?

Preparation and characterization of the first examples of copper(I) ferrocenylpolyphosphine complexes are reported. The molecular structure of complex {P,P′,P′′-[1,1′,2,2′-tetrakis(diphenylphosphino)-4,4′-di-tert-butylferrocene]iodocopper(I)} (1) was solved by X-ray diffraction studies, and its fluxional behavior in solution was investigated by VT-31P NMR; both revealed a net triligated coordination preference of the ferrocenyl tetraphosphine Fc(P)4tBu with copper. The tetradentate ligand is an active auxiliary in Sonogashira alkynylation; therefore the general question of copper as a competitive coordination partner in the Pd/Cu-catalyzed Sonogashira reaction was raised and discussed. Elec…

Amino-phosphanes in RhI-Catalyzed Hydroformylation: Hemilabile Behavior of P,N Ligands under High CO Pressure and Catalytic Properties

International audience; The catalytic properties of rhodium complexes containing the α-, β-, or γ-amino-phosphane ligands Ph2PCH2NEt2 (α-P,N-1), Ph2PCH(Ar)NHPh [α-P,N-2; Ar = η6(o-C6H4Cl)Cr(CO)3], Ph2PCH2NPh2 (α-P,N-3), Ph2PCH2CH(Ph)NHPh (β-P,N), Ph2PCH2(o-C6H4–NMe2) (γ-P,N-1), Ph2PCH(o-C6H4–CH2NHPh) (γ-P,N-2), and the α,β-diamino-phosphane ligand Et2NCH2P(Ph)CH2CH(Ph)NHPh (α,β-N,P,N), in styrene hydroformylation have been examined. The results show that the activity increases when the number of backbone carbon atoms linking P and N decreases from 3 to 1. IR and 31P HPNMR studies in solution show that all P,N ligands adopt exclusively a κ1-P coordination mode in rhodium chloride carbonyl co…

Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a “Smart” Probe Answer!

Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. …

Gold( i )–BODIPY–imidazole bimetallic complexes as new potential anti-inflammatory and anticancer trackable agents

International audience; Two new gold(I)–BODIPY–imidazole based trackable therapeutic bimetallic complexes have been synthesized and fully characterized. They display strong antiproliferative properties on several types of cancers including colon, breast, and prostate and one of them presents a significant anti-inflammatory effect. Additionally, the two compounds could be visualised in vitro by confocal microscopy in the submicromolar range.

Further synthetic and structural investigations of new pre-organized picket porphyrins

The straightforward synthesis of three new picket porphyrins with a restrained conformation is described. These porphyrins have an unusual behavior due to the conjugated but still flexible nature of their pickets. The crystal structure of their common precusor is also reported and confirms the presumed geometry of this type of picket. Indeed, the latter one is formally obtained by the conjugation of two aromatic rings through an amide bond. Although the specific shape of the picket is expected to overcrowd the center of the porphyrin, it is shown that different types of nucleophilic reagents can add easily on these pickets.

A Simple Phosphine–Diolefin‐Promoted Copper‐Catalysed N‐Arylation of Pyrazoles with (Hetero)aromatic Bromides: The Case of Chloroarenes Revisited

A molecularly defined new phosphine–diolefin cubane copper pre-catalyst used at 1.25 mol % under mild conditions promotes the coupling of pyrazoles to functionalised aryl and heteroaryl bromides, which hold a variety of functional groups. This versatile phosphorus-based system was thus successfully used, under identical conditions, for the coupling of a large scope of heteroaromatics to selectively produce pyridinyl- and pyrimidinyl-pyrazoles, as well as several novel furyl-, thienyl- and thiazolyl-substituted pyrazoles. The careful investigation of coupling with the analogous aryl and heteroaryl chlorides clearly indicated that for specifically activated chloroarenes a direct nucleophilic …

Reappraising Schmidpeter's bis(iminophosphoranyl)phosphides: coordination to transition metals and bonding analysis

The synthesis and characterization of a range of bis(iminophosphoranyl)phosphide (BIPP) group 4 and coinage metals complexes is reported. BIPP ligands bind group 4 metals in a pseudo fac-fashion, and the central phosphorus atom enables the formation of d0–d10 heterobimetallic complexes. Various DFT computational tools (including AIM, ELF and NCI) show that the phosphorus–metal interaction is either electrostatic (Ti) or dative (Au, Cu). A bridged homobimetallic Cu–Cu complex was also prepared and its spectroscopic properties were investigated. The theoretical analysis of the P–P bond in BIPP complexes reveals that (i) BIPP are closely related to ambiphilic triphosphenium (TP) cations; (ii) …

CCDC 1868748: Experimental Crystal Structure Determination

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CCDC 1871410: Experimental Crystal Structure Determination

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CCDC 1014064: Experimental Crystal Structure Determination

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CCDC 1578513: Experimental Crystal Structure Determination

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CCDC 987356: Experimental Crystal Structure Determination

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CCDC 1978292: Experimental Crystal Structure Determination

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CCDC 1871415: Experimental Crystal Structure Determination

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CCDC 1555141: Experimental Crystal Structure Determination

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CCDC 1871416: Experimental Crystal Structure Determination

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CCDC 1978293: Experimental Crystal Structure Determination

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CCDC 1578514: Experimental Crystal Structure Determination

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CCDC 1828666: Experimental Crystal Structure Determination

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CCDC 1871408: Experimental Crystal Structure Determination

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CCDC 881688: Experimental Crystal Structure Determination

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CCDC 1825467: Experimental Crystal Structure Determination

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CCDC 1053357: Experimental Crystal Structure Determination

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CCDC 1825466: Experimental Crystal Structure Determination

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CCDC 1868745: Experimental Crystal Structure Determination

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CCDC 1978288: Experimental Crystal Structure Determination

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CCDC 1978291: Experimental Crystal Structure Determination

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CCDC 1456530: Experimental Crystal Structure Determination

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CCDC 1978295: Experimental Crystal Structure Determination

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CCDC 1985146: Experimental Crystal Structure Determination

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CCDC 1985142: Experimental Crystal Structure Determination

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CCDC 1825460: Experimental Crystal Structure Determination

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CCDC 1868749: Experimental Crystal Structure Determination

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CCDC 1985138: Experimental Crystal Structure Determination

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CCDC 1978290: Experimental Crystal Structure Determination

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CCDC 1978289: Experimental Crystal Structure Determination

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CCDC 1052598: Experimental Crystal Structure Determination

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CCDC 1985136: Experimental Crystal Structure Determination

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CCDC 1009630: Experimental Crystal Structure Determination

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CCDC 1438419: Experimental Crystal Structure Determination

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CCDC 1009631: Experimental Crystal Structure Determination

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CCDC 1825463: Experimental Crystal Structure Determination

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CCDC 1052596: Experimental Crystal Structure Determination

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CCDC 1502145: Experimental Crystal Structure Determination

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CCDC 987359: Experimental Crystal Structure Determination

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CCDC 1871418: Experimental Crystal Structure Determination

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CCDC 1871412: Experimental Crystal Structure Determination

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CCDC 1828665: Experimental Crystal Structure Determination

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CCDC 1825459: Experimental Crystal Structure Determination

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CCDC 1052597: Experimental Crystal Structure Determination

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CCDC 1871414: Experimental Crystal Structure Determination

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CCDC 1052593: Experimental Crystal Structure Determination

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CCDC 1578510: Experimental Crystal Structure Determination

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CCDC 1555144: Experimental Crystal Structure Determination

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CCDC 1868747: Experimental Crystal Structure Determination

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CCDC 1985140: Experimental Crystal Structure Determination

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CCDC 977462: Experimental Crystal Structure Determination

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CCDC 1978287: Experimental Crystal Structure Determination

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CCDC 1053358: Experimental Crystal Structure Determination

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CCDC 1825465: Experimental Crystal Structure Determination

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CCDC 1438417: Experimental Crystal Structure Determination

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CCDC 987357: Experimental Crystal Structure Determination

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CCDC 1937786: Experimental Crystal Structure Determination

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CCDC 1985143: Experimental Crystal Structure Determination

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CCDC 1555142: Experimental Crystal Structure Determination

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CCDC 1871411: Experimental Crystal Structure Determination

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CCDC 1420553: Experimental Crystal Structure Determination

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CCDC 1014822: Experimental Crystal Structure Determination

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CCDC 1578511: Experimental Crystal Structure Determination

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CCDC 1538131: Experimental Crystal Structure Determination

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CCDC 1052592: Experimental Crystal Structure Determination

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CCDC 987358: Experimental Crystal Structure Determination

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CCDC 1871409: Experimental Crystal Structure Determination

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CCDC 1578512: Experimental Crystal Structure Determination

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CCDC 1052595: Experimental Crystal Structure Determination

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CCDC 1555143: Experimental Crystal Structure Determination

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CCDC 1009629: Experimental Crystal Structure Determination

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CCDC 1014823: Experimental Crystal Structure Determination

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CCDC 1052594: Experimental Crystal Structure Determination

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CCDC 1825462: Experimental Crystal Structure Determination

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CCDC 1871417: Experimental Crystal Structure Determination

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CCDC 1978294: Experimental Crystal Structure Determination

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CCDC 1825461: Experimental Crystal Structure Determination

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CCDC 1825458: Experimental Crystal Structure Determination

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CCDC 1438418: Experimental Crystal Structure Determination

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CCDC 1985135: Experimental Crystal Structure Determination

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CCDC 1420552: Experimental Crystal Structure Determination

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CCDC 1868750: Experimental Crystal Structure Determination

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CCDC 1985137: Experimental Crystal Structure Determination

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CCDC 1985139: Experimental Crystal Structure Determination

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CCDC 1035220: Experimental Crystal Structure Determination

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CCDC 977461: Experimental Crystal Structure Determination

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CCDC 882546: Experimental Crystal Structure Determination

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CCDC 1825464: Experimental Crystal Structure Determination

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CCDC 1443023: Experimental Crystal Structure Determination

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CCDC 1985134: Experimental Crystal Structure Determination

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CCDC 1472956: Experimental Crystal Structure Determination

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CCDC 1868746: Experimental Crystal Structure Determination

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CCDC 1868743: Experimental Crystal Structure Determination

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CCDC 1056295: Experimental Crystal Structure Determination

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CCDC 1985141: Experimental Crystal Structure Determination

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CCDC 1578509: Experimental Crystal Structure Determination

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CCDC 1985144: Experimental Crystal Structure Determination

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