Tungsten thiolate complexes

This particular thiocarbenoid complex and the analogous tungsten derivative are more conveniently synthesized by an initial reaction of [Cr(CO)5 C(CH3)(OCH3) ] or [W(CO)5 C(CH3)(OCH3) ] with benzene-thiolate ion at room temperature followed by acidification with hydrochloric acid. This synthetic route has also been used to prepare a series of pentacarbonyl[(l-phenylthio)ethylidene]tungsten(0) complexes substituted in the 4-position of the phenyl rings.4... 

An interesting series of molybdenum and tungsten hydride complexes with sterically hindered thiolate ligands has recently been established due to the interest in their possible relevance to hydrodesulfurization catalysis and to the active site of the enzyme nitrogenase. The complexes [MH(SAr)3(PMe2Ph)2l (M = Mo, W SAr = TIPT, TMT) were prepared as summarized in Eqs. (8) and (9). 

The monomeric tungsten(IV) phenoxide and thiolate complexes [W(0-2,6-C6H3R2)]4] (R = Me, /-Pr) and [W(S-t-Bu)4] were produced by the reaction of [WCl4(Et2S)2] and the corresponding phenolate or thiolate anion.133,134 The phenolate complexes exhibited nearly square planar geometry. 

Fulvalenes, with bis-Cp Ti(IV), 4, 587 Fulvalene thiolates, in tungsten carbonyl and isocyanide complexes, 5, 644... 

The heterometallacyclic alkyne-containing complex 85 (M = Mo or W, R = Pr or /7-MeQH4, R = Me or Ph) isomerizes into 86 above 20°C (90). At 55°C the tungsten compound with R being Pr and R Ph rearranges, with incorporation of the alkyne ligand into a metallacycle and extrusion of the thiolate from the chelate ring, to form 87. 

Dinitrogen complexes of molybdenum and tungsten with mono-, di - and tii - tertiary phosphine co -ligands are electrosynthesised from molecular nitrogen andMo or precursors vw cleavage of halide or thiolate bonds and from Mo or oxide, imide or hydrazide complexes by... 

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