Chemistry of di- and tri-metal complexes with bridging carbene or carbyne ligands. Part 20. Complexation of carbon–metal triple bonds with low-valent metal species; crystal structures of the bimetal complexes [CrW(µ-CC6H4Me-4)(CO)4(η-C5H5)(η-C6Me6)] and [CoW(µ-CC6H4Me-4)(CO)3(η-C5H5)(η-C5Me5)]

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Abstract
A series of bimetal complexes [MW(µ-CR)(CO)2(Ln)(η-C5H5)][R = C6H4Me-4; MLn= Cr(CO)2(η-C6Me6), Mn(CO)2(η-C5H4Me), Re(CO)2(η-C5H5), Co(CO)(η-C5Me5), Rh(CO)(η-C9H7)(C9H7= indenyl), lr(CO)(η-C9H7), and Ir(CO)(acac)(acac = acetylacetonate)] have been prepared from [W(CR)(CO)2(η-C5H5)] and [Cr(CO)2(thf)(η-C6Me6)](thf = tetrahydrofuran), [M(CO)2(thf)(C5H4R′)](M = Mn, R′= Me; M = Re, R′= H), [Co(CO)2(η-C5Me5)], [M(CO)2(η-C9H7)](M = Rh or Ir), and [Ir(acac)(CO)2], respectively. The compounds [RhW(µ-CMe)(CO)3(η-C5H5)(η-C9H7)] and [MoRh(acac)(µ-CMe)(CO)3(η-C5H5)] have also been obtained from related reactions. The spectroscopic data (i.r. and n.m.r.) for the new compounds are reported and discussed. The structures of the species [CrW(µ-CR)(CO)4(η-C5H5)(η-C6Me6)], (1) and [CoW(µ-CR)(CO)3(η-C5H5)(η-C5Me5)](4) have been established by X-ray diffraction, and reveal an interesting distinction between (1) and (4). For both structures the metal–metal bond is bridged by a CC6H4Me-4 group and is semi-bridged by a CO ligand, but whereas in (4) it is one of the CO ligands on the W atom which semi-bridges to Co, in (1) it is a CO ligand on the Cr atom which semi-bridges to W. Reasons for this are discussed. In both structures the cyclic ligands bonded to the metal atoms are in a trans configuration with respect to the [graphic omitted] plane.

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