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.
Bibliographical noteFunding Information:
We acknowledge support of this research by the donors of the Petroleum Research Fund, administered by the American Chemical Society and the National Science Foundation. Portions of this manuscript are based on the MS. Thesis of T.G. Hayes, University of Minnesota (1979) and the Undergraduate Senior Thesis of R.E. Stevens, University of Wisconsin-Madison (1980). We are grateful to Professor L-F. DahI, University of Wisconsin-Madison, for his support and advice concerning the crystallographic work described herein.