Bioinspired Catalysis, Metal-Sulfur Complexes

International audiencehis book provides an overview of bioinspired metal-sulfur catalysis by covering structures, activities and model complexes of enzymes exhibiting metal sulphur moieties in their active center

Bio-inspired hydrogen production/uptake catalysis

International audienceIt was a great pleasure for us to accept the invitation of Pierre Braunstein, Editor-in-Chief of the Comptes Rendus Chimie , to guest-edit this thematic issue. We chose to devote it to an exciting field of research, which concerns the production and the oxidation of hydrogen by bio-inspired catalysts. Indeed, the development of economic and ecological processes of hydrogen production/uptake is a major goal in the perspective of a hydrogen economy. This thematic issue, entitled Bio-inspired hydrogen production/uptake catalysis , is dedicated to the chemists' efforts, in this multidisciplinary field at the interface of chemistry and biology, to conceive and to study new molecules inspired by the active sites of the [NiFe] and [FeFe] hydrogenases. The ultimate purpose of these theoretical and experimental studies is to achieve efficient electrocatalysts for the production or the oxidation of hydrogen through a better understanding of the mechanisms implied at the molecular level. We thank Pierre Braunstein very warmly for his invitation, as well as all the colleagues whose contributions allowed the edition of this thematic issue, which, we hope, will contribute to illustrate different aspects of the research performed by chemists in this challenging field

Contribution à l'étude de complexes organométalliques dinucléaires du molybdène à environnement soufré pour l'activitaion moléculaire (réactivité vis à vis d'alcynols, d'isocyanures et de molécules soufrées)

Les complexes organométalliques possédant un environnement soufré font l objet, depuis plusieurs années, de nombreuses études qui ont démontré les capacités de ces dérivés à activer de nombreux substrats organiques ou inorganiques. Les travaux qui ont été menés au cours de cette thèse s inscrivent dans la continuité du développement de la chimie des systèmes dimolybdène thiolato-pontés {Mo2Cp2( -SMe)n}+ (n=2,3) qui est réalisée dans le laboratoire afin d évaluer l apport de ces systèmes pour l activation moléculaire. Dans une première partie, nous présentons nos résultats concernant la coordination et la transformation d alcools propargyliques par le complexe [Mo2Cp2( -SMe)3(CH3CN)2] (BF4). Nous décrivons la synthèse puis la transformation de composés -alcyne en complexes -allénylidène. La réactivité des dérivés -allénylidène avec des agents nucléophiles ainsi que les réactions de transferts successifs d hydrures et de protons sur ces dérivés sont également décrites. Le second chapitre du manuscrit est consacré à la transformation de ligands isocyanure par action de réactifs basiques ou/et nucléophiles comme NaOH, NaSH et NaCCH. En particulier, des réactions permettant l obtention, via des processus impliquant la formation de liaisons C-C, C-N ou C-O, d espèces comportant des ligands alkylidyne et amino-oxycarbène sont décrites. La troisième partie de ce travail concerne la réactivité du complexe [Mo2Cp2( -SMe)3(CH3CN)2](BF4) avec des molécules hétérocycliques soufrées. Des transformations mettant enjeu la substitution des ligands acétonitrile mais également la formation et la rupture de liaisons C-S ont été mises en évidence. L ensemble de ces résultats montre la richesse et l originalité des systèmes du dimolybdène utilisés.We have been involved for some years in sulfur rich bimetallic systems which can act as models of species occuring in biological and industrial processes. Our approach implied organometallic complexes containing the bimetallic core {Mo2Cp2( -SMe)3}, which react with unsatured molecules such as alkyne, isocyanide, nitrile... Complexes with alkynol ligands bridging two metals have been isolated and characterised. Further transformations of Mo2-alkynol adducts to allenylidene species were also obtained, and the conversion of the former into an agostic ligand was observed. At the same time, we described the reactivity of isonitrile towards nucleophilic agents (NaOH, NaSH or NaCCH), leading to new compound containing ligands such as aminocarbyne, aminocarbene and aminooxycarbene which result either from C-C and C-N couplings between the cyclopentadienyl ligand and isocyanides or from C-C coupling between isocyanide groups. Moreover, the syntheses and characterisation of Mo complexes containing sulfide, thioether, dithiane and thioxane were carried out. These reactions are of interest in connection with the modeling of catalytic hydrodesulfuration (HDS) processes. Finally, we described here the syntheses of new complexes and original transformations promoted by a bimetallic molybdenum core.BREST-BU Droit-Sciences-Sports (290192103) / SudocSudocFranceF

Modulation of S‐Centered Reactivity: Impact of Terminal Ligands on Alkynyl Addition in [Fe2(µ‐S2)(CO)4L2] Complexes

International audienceThe reactivity of complexes [Fe2(µ‐S2)(CO)4L2] (L = CO (1), PPh3 (2)), with lithium alkynylide reagents generated in situ, was investigated. The behavior of the S2‐bridge in these compounds depends on the substitution at the diiron core. The reaction with the hexacarbonyl derivative 1 leads to the formation of the 1,2‐dithiolene bridged complex [Fe2(µ‐SCH=C(R)S)(CO)6] (3R) while the molecule [Fe2(µ‐SH)(µ‐SC≡CR)(CO)4(PPh3)2] (5R), with an open butterfly structure, is isolated when reacting the disubstituted derivative 2. The disubstituted dithiolene complex [Fe2(µ‐SCH=C(Ph)S)(CO)4(PPh3)2] (4Ph) can only be obtained by substitution of carbonyls with PPh3 in 3R. In the presence of piperidine, 5R isomerizes into the 1,1’‐dithiolene bridged derivative 6Ph. The novel compounds 4‐6 were synthesized and characterized by IR and NMR spectroscopies. X‐ray crystallographic studies of the dithiolene complexes 3Ph‐4Ph allowed their structural analysis

Triiron Complexes Featuring Azadiphosphine Related to the Active Site of [FeFe]-Hydrogenases: Their Redox Behavior and Protonation

The design of iron clusters featuring a bimetallic core and several protonation sites in the second coordination sphere of the metal centers is important for modeling the activity of polymetallic active sites such as the H-cluster of [FeFe]-hydrogenases. For this purpose, the syntheses of complexes [Fe3(CO)5(κ2-PPh2NR2)(μ-pdt)2] (R = Ph (1), Bn (2)) and [Fe3(CO)5(κ2-PPh2NR2)(μ-adtBn)(μ-pdt)] (R = Ph (3), Bn (4)) were carried out by reacting hexacarbonyl precursors [Fe2(CO)6(µ-xdt)] (xdt = pdt (propanedithiolate), adtBn (azadithiolate) with mononuclear complexes [Fe(κ2-pdt)(CO)2(κ2-PPh2NR2)] (PPh2NR2 = (PPhCH2NRCH2)2, R = Ph, Bn) in order to introduce amine functions, through well-known PPh2NR2 diphosphine, into the vicinity of the triiron core. The investigation of the reactivity of these triiron species towards the proton (in the presence of CF3SO3H) and the influence of the pendant amines on the redox properties of these complexes were explored using spectroscopic and electrochemical methods. The protonation sites in such triiron clusters and their relationships were identified. The orientation of the first and second protonation processes depends on the arrangement of the second coordination sphere. The similarities and differences, due to the extended metal nuclearity, with their dinuclear counterparts [Fe2(CO)4(κ2-PPh2NR2)(μ-pdt)], were highlighted

Reactions of di- and polynuclear complexes. VIII. Ligand substitution in [V2Cp2(CO)4(μ-SMe)2] by isocyanides or trimethyl phosphite. Synthesis, spectroscopic characterisation of the mono- and di-substituted derivatives. Electrochemical behaviour of the parent complex

International audienceThe photo-induced decarbonylation of [VCp(CO)4] in the presence of an organodisulfide RSSR (R = Ph) or a thiol HSR (R = nPr, tBu, Et) at room temperature in THF gives the binuclear diamagnetic compounds [V2Cp2(CO)4(μ-SR)2] (1). Thermal substitution of RNC (R = tBu, xylyl) for CO in 1 results in the formation of a mixture of isomeric mono- and di-substituted derivatives [V2Cp2(CO)3(CNR)(μ-SMe)2] (3) and [V2Cp2(CO)2(CNR)2(μ-SMe) 2] (4), respectively. The complexes have been characterised by infrared and 1H NMR spectroscopies. The primary reduction of [V2Cp2(CO)4(μ-SMe)2] is a partially reversible one-electron step coupled with chemical reactions. The nature of these reactions and of the product of controlled-potential electrolyses are discussed. © 1991

Role of a Redox-Active Ligand Close to a Dinuclear Activating Framework

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