SIX- AND SEVEN-COORDINATE MAIN GROUP IV METAL DERIVATIVES OF PENTACARBONYLVANADATE(3-) ION. STRUCTURAL CHARACTERIZATION OF TETRAETHYLAMMONIUM BIS(TRIPHENYLSTANNYL)PENTACARBONYLVANADATE

Article abstract of DOI:10.1016/S0022-328X(00)85760-5

Organotin and triphenyllead derivatives (Ph3Sn)2V(CO)5^-, ((C6H11)3Sn)(Ph3Sn)V(CO)5^-, (Me3Sn)(Ph3Sn)V(CO)5^- and (Ph3Pb)2V(CO)5^- containing seven-coordinate vanadium have been isolated as tetraethylammonium salts in 40-80percent yields from the reactions of appropriate organometal halides with Ph3EV(CO)5^2- (E=Sn, Pb).The latter have been prepared by the reduction of <(Ph3E)2V(CO)5> and are the first reported organotin and -lead metal carbonyl derivatives which contain a transition metal in a formal negative oxidation state.The crystal structure of <(Ph3Sn)2V(CO)5>, which is synthesized in low yields (ca. 15percent) from the photolysis of in the presence of Ph6Sn2, has been determined by single crystal X-ray diffraction techniques.The anion contains two Sn-V bonds with a Sn-V-Sn angle of 137.9(1) deg.Its geometry is discussed in terms of three possible seven-coordination environments.