CARBONYL AND PHOSPHINE ADDUCTS OF OPEN TITANOCENES AND OPEN VANADOCENES - SYNTHESES, SPECTROSCOPIC STUDIES, AND SOLID-STATE STRUCTURES

The syntheses of a variety of 17-electron open vanadocene adducts are reported, incorporating a variety of pentadienyl (Pdl = C5H7, 1-, 2-, or 3-C6H9, 2,3-C7H11, 2,4-C7H11) and additional ligands (CO, dmpe, PX3; X = F, OCH3, CH3, C2H5). Also prepared for comparison are the carbonyl adducts of Ti(C5H7)2 and Ti(3-C6H9)2. Spectroscopic and structural data are in accord with the adoption of symmetric syn-eclipsed structures in all cases. Single-crystal structure determinations have been carried out for several V(Pdl)2CO complexes. For Pdl = 1-C6H9, the space group is P42(1)cBAR, with a = b = 19.173 (8) angstrom, c = 6.753 (2) angstrom, and Z = 8. For Pdl = 2,4-C7H11, the space group is P2(1)2(1)2(1), with a = 9.933 (6), b = 10.013 (5), and c = 14.612 (7) angstrom for Z = 4, while, for Pdl = 3-C6H9, the space group is Pbca, with a = 11.179 (4), b = 14.016 (5), and c = 15.797 (5) angstrom for Z = 8. A variety of infrared and ESR spectral studies have been carried out to help probe the electronic natures of these compounds.