SYNTHESES, CHARACTERIZATION, AND STRUCTURAL STUDIES OF LEWIS BASE ADDUCTS OF HALF-OPEN VANADOCENES, V(C5H5)(PDL)(L)

A variety of mono(ligand) adducts of half-open vanadocenes, V(C5H5)(Pdl)(L), have been prepared from V(C5H5)Cl2(PEt3)2 or V(C5H5)I2 and various pentadienyl anions (Pdl = C5H7, 3-C6H9, 2,4-C7H11; L = PEt3, PMe3, P(C6H5)3, dmpe/2). Other ligand adducts (L = CO, PF3, P(OMe)3, P(OC6H5)3, P(OCH2)3CCH3, CN(t-C4H9)) may also be prepared, by a replacement of PEt3 from the appropriate V(C5H5)(Pdl)(PEt3) COMPlex. These species have been characterized by infrared and ESR spectroscopic studies, as well as magnetic susceptibility measurements and single-crystal structural determinations. Crystals of V(C5H5)(C5H7)(CO) are monoclinic, space group P2(1)/n, with a = 11.821(4) angstrom, b = 8.109(2) angstrom, c = 20.309(5) angstrom, beta = 93.96(2)-degrees, and V = 1942.0(9) angstrom for z = 8, while crystals of V(C5H5)(C5H7)(PEt3) are also monoclinic, space group P2(1)/c, with a = 14.999(5) angstrom, b = 7.710(2) angstrom, c = 14.290(7) angstrom, beta = 101.59(3)-degrees, and V = 1618.9(11) angstrom3 for Z = 4.