REACTIONS OF PHOSPHINE-SUBSTITUTED ALKYLIDYNE CARBONYLTUNGSTEN COMPLEXES WITH DITHIOCARBAMATE LIGANDS - PHOSPHINE SUBSTITUTION AND ALKYLIDYNE CARBONYL COUPLING

Reaction of the alkylidyne tungsten complexes cis- and trans- [W(CPh)C l(CO)2(PMe3)2] with sodium diethyldithiocarbamate affords the ketenyl complex [W(OCCPh)(S2CNEt2)(CO)(PMe3)2]. Reaction of [W(CPh)Cl(CO)(PMe3 )3] with diethyldithiocarbamate gives the dithiocarbamate-substituted alkylidyne tungsten complex [W(CPh)(S2CNEt2)(CO)(PMe3)2]. Reaction of cis-[W(CPh)Cl(CO)2(PPh3)2] with sodium dimethyldithiocarbamate leads t o substitution of PPh3 and formation of [W(CPh)(S2CNMe2)(CO)2(PPh3)]. The solid state structure of [W(CPh)(S2CNEt2)(CO)(PMe3)2] was determin ed by X-ray crystallography. Reaction of [W(CPh)(S2CNEt2)(CO)(PMe3)2] with carbon monoxide in solution as well as in the solid state affords [W(OCCPh)(S2CNEt2)(CO)(PMe3)2]. Pyrolysis of [W(OCCPh)(S2CNEt2)(CO)(P Me3)2] at 100-degrees-C in toluene solution gives [W(CPh)(S2CNEt2)(CO) (PMe3)2].