Tungsten thiocarbyne complex

The tungsten thiocarbyne complex 171 is attacked by PRj (R = Me, Et) at the carbyne carbon atom (164). Templeton and co-workers found that with PEtj the phosphonium carbyne complex 172 is obtained [Eq. (141)] whereas reaction with PMcj gives the bisphosphonium carbene complex 173 [Eq. (142)]. One PMej appears to be able to dissociate from 173, and... 

Electrophilic addition to the sulfur atom of terminal thiocarbonyl ligands is a well-established route to thiocarbyne complexes of Group VI metals [2, 18, 19]. A requirement for the success of this approach is that the thiocarbonyl ligand be bound to a very electron-rich metal centre, preferably in an anionic complex. A methyltellurocarbyne complex of tungsten, [L(CO)2W=CTeMe]... 

Reaction of the thiocarbyne TpW( = CSMe)(CO)2 with the Ni(I) dimer Cp2Ni2(At-CO)2 generates a trinuclear metal complex based on a Ni2W triangle TpCp2WNi2(/t3-CSMe)(CO)2 (Scheme 71). Two infrared stretches at 1875 and 1806 cm are consistent with a semi-bridging role for the tungsten carbonyls. 

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