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 40-80% yields from the reactions of appropriate organometal halides with Ph3EV(CO)52- (E = Sn, Pb). The latter have been prepared by the reduction of [Et4N] [(Ph3E)2V(CO)5] and are the first reported organotin and -lead metal carbonyl derivatives which contain a transition metal in a formal negativ oxidation state. The crystal structure of [Et4N] [(Ph3Sn)2V(CO)5], which is synthesized in low yields (ca. 15%) from the photolysis of [Et4N] [V(CO)6] in the presence of Ph6Sn2, has been determined by single crystal X-ray diffraction techniques. The anion contains two SnV bonds with a SnVSn angle of 137.9(1)°. Its geometry is discussed interms of three possible seven-coordination environments.