Jean-Yves Le Marouille

Ferrocenyltrithiocarbonates : II. Synthesis and x-ray structure determination of diiron hexacarbonyl complexes

Abstract Ferrocenyltrithiocarbonates, I, react with Fe2(CO)9 to afford new types of binuclear complexes in which the diiron hexacarbonyl moiety is linked by two bridges resulting from the insertion of an iron atom into the carbon-sulfur single bond. The X-ray structure determination of μ-(thioferrocenylmethylmethane thiomethylene-C1, S2)-1,1,1,2,2,2-hexacarbonyl-μ-methylthioiron (FeFe) has been refined to R = 0.037. Comparison of X-ray and 13C data with those of the starting materials are in agreement with a metallocarbene structure.

Nouvell préparation, propriétés electrochimiques et etude structurale des phosphaferrocenes η5-C5Me5Fe-η5-PC4(R4)

Abstract A new synthesis of phosphaferrocenes is described. It involves nucleophilic attack of a phospholyl anion on a metastable cyclopentadienyliron acetylacetonate. The monoelectronic oxidation of the phosphaferrocenes thus obtained has been studied by cyclic voltammetry in various solvents. The X-ray structures of [η 5 -C 5 Me 5 Fe-η 5 -PC 4 (C 6 H 5 ) 4 ] is discussed and compared with the structure of [η 5 -C 5 H 5 Fe-η 5 -PC 4 H 2 (CH 3 ) 2 ].

Complexation d'iminopyridines par le sel de zeise: voie d'access a des conjugues estradiol-cis-dichloro platine. Etude structure du complexe cis-PtCl2[C5H4NCH2NC(CH3)C6H4OH],H2O

Abstract In order to synthesize penta- and hexa-gonal platinum(II) metallocycles, bidentate ligands such as iminopyridines (L) have been prepared and characterized. The (2-pyridyl)CHNR 1 and (2-pyridyl)CH 2 NCR 1 R 2 ligands react with Zeises salt to afford directly the pentagonal chelates PtCl 2 L. Their structure and the cis -stereo-chemistry were shown by the usual spectroscopic methods and for cis -PtCl 2 [C 5 H 4 NCH 2 NC(CH 3 )C 6 H 4 OH],H 2 O by an X-ray diffraction study. On the other hand, the (2-pyridyl)(CH 2 ) 2 NCR 1 R 2 ligands do not afford the expected hexagonal metallocycles; instead, after complexation at the nitrogen atom of the imine they give rise to the (2-pyridyl)ethylamine complex formed after hydrolysis of the coordinated ligands. Complexes trans -[ethylene][(2-pyridyl)(CH 2 ) 2 NCR 1 R 2 ]PtCl 2 represent when R 1 is estradiol a model for “cytotoxic with delayed activity”.

Substitution selectives de carbonyles dans des complexes polynucleaires V. Etudes Structurales des composes de mono-et disubstitution de co par P(OMe)3 dans un complexe binucleaire non symetrique

Abstract The complexes μ-(alkoxymethanethione- C , S -μ-(methylthio)-1-trimethylphosphite-1,1,2,2,2,-pentacarbonyldiiron (II) are obtained by controlled replacement of CO by P(OMe) 3 in the hexacarbonyl precursors I. The structure of the complex IIa (alkoxy-adamantylmethoxy) has been determined by single-crystal X-ray diffraction. The structure shows that P(OMe) 3 has replaced one carbonyl on Fe(1) and occupies an equatorial position placing it in cis relationship with the carbene C(1) and the two carbonyls coordinated to Fe(1). Knowledge of the structures I and II allows one to elucidate their 13 C NMR spectra in the carbene and carbonyl regions. For instance 2 J and 3 J coupling constants and chemical shifts for these ligands can be proposed on the basis of bond lengths and on the dynamic behavior of compounds I and II for which the fluxionality is limited to the ligands coordinated to Fe(2). These data allow one to propose the structure of the bis-phosphite complexes III and of hte isomeric monophosphite IVa, obtained when the monosubstitution is carried out by electron transfer catalysis.

Synthesis and structure of the first diamagnetic trinuclear cobalt carbonyl sulfur complexes, SCo3(CO)7(μ-R1ĆNR2)

Abstract Reaction of primary thioamides with dicobalt octacarbonyl affords in good yield the first diamagnetic monomeric trinuclear cobalt carbonyl sulfur complexes SCO 3 (CO) 7 (μ-R 1 CNR 2 ), which contain a bridging bidentate imino ligand. The structure of the product with R 1  Me, R 2  C 6 H 11 has been determined by X-ray diffraction, and shown to include a very short cobaltcobalt bond distance and a long cobaltsulfur bond distance when compared to other cobaltsulfur clusters.

Synthesis and X-ray structure of [RuCo3(µ-CO)2(CO)7(µ-PPh2)(µ4-η2-ButCCH)]: a novel heteronuclear butterfly cluster via the fragmentation of a phosphinoalkyne

The dehalogenation of [RuCl2(Ph2PCCBut)(p-cymene)](1) by Co2(CO)8 and subsequent protonation afford the mixed metal cluster [RuCo3(µ4-η2-ButCCH)(µ-PPh2)(CO)9](2) for which an X-ray structure determination has established the butterfly configuration of the RuCo3 species.

A new diamagnetic trinuclear cobalt carbonyl-sulfur complex with a bridging thiocarboxamido group, SCo3(CO)7(CSNMe2)

Abstract Reaction of dimethylthiocarbamoyl chloride or dimethylthioformamide with dicobalt octacarbonyl affords a new diamagnetic trinuclear cobalt carbonyl-sulfur complex SCo3(CO)7(CSNMe2) containing a bridging bidentate thiocarboxamido ligand liked to the cluster by a cobalt—carbon and a cobalt—sulfur bond. The structure has been determined by X-ray diffraction; comparison with the recently described SCo3(CO)7(μ-R1C-NR2) shows a different electronic distribution in the cluster and in the bridge, with important participation of the nitrogen atom.

Complexes binucleaires de fer carbonyle liaison σ-metal-carbone: Synthese, etude structurale et proprietes

Abstract Dithioesters R1C(S)SR2 react with [Fe2(CO)9] to afford binuclear complexes (Co)3FeC(R1)S(R2)SFe(CO)3 (I) in which the organic ligand gives six electrons to the Fe2(CO)6 skeleton. Spectroscopic data show the existence of carboniron σ bond with creation of a chiral center. This is confirmed by single-crystal X-ray structure determination of complex Ig(R1 = C4H3S, R2 = Me). This structure shows that coordination imposes important geometrical constraints. 13C NMR studies reveal a temperature dependant dynamic behaviour for complexes I in solution. The carbonyl fluxionality occurs around each metal atom independently. Electrophilic substitution of the coordinated organic ligand may occur despite the complex fragility in a basic medium or in the presence of oxidizing agents.

New oxovanadium complexes coordinated to a fac-tridentate organometallic ligand and X-ray crystal structure of [η-CpCo{P(O)(OC2H5)2}3VO(acac)]: Their role in oxidative catalysis

Abstract Treatment of VO(acac) 2 with the facial-tridentate organometallic ligand [η-CpCo{P(O)(OEt) 2 } 3 ] − affords a new binuclear compound [η-CpCo{P(O)(OEt) 2 } 3 VO(acac)] (I). This compound undergoes protonation with HPF 6 in the presence of 1,10-phenanthroline (phen), or 2,2′-bipyridyl (bipy), to yield binuclear cationic derivatives [η-CpCo{P(O)(OEt) 2 } 3 VO(phen))] + PF 6 − (II), and [η-CpCo{P(O)(OEth) 2 } 3 VO(bipy)] + PF 6 − (III). The X-ray crystal structure determination and full characterization of I has been performed. The catalytic oxygenation and oxygen transfer to 3,5-di-t-butylcatechol in the presence of I, II + , or III + complexes is reported.

Ferrocenyltrithiocarbonates : I. Direct access from α-ferrocenylcarbinols by a SNi mechanism. Absolute x-ray structure determination of (R)-ferrocenylmethylmethane S-methyl-trithiocarbonate

Resume Ferrocenyltrithiocarbonates (I) are readily obtained by treating α-ferrocenylcarbinols (II) successively with sodium hydride, carbon disulfide and alkyl halide. Formation of I occurs by intramolecular nucleophilic displacement of oxygen by sulfur with retention of configuration. This is supported by the nature of the other products formed and by the X-ray structure determination of an optically active compound I, which was refined to R  0.038. The title compound of R configuration was obtained from ( R )-ferrocenylmethyl-methanol.