HETERODINUCLEAR TITANIUM COBALT COMPLEXES - SYNTHESES AND PROPERTIES - X-RAY STRUCTURE OF [(TC4H9O)3TICO(CO)4] (TI-CO)

An X-ray structural investigation establishes an unbridged Ti-Co bond in [(tC4H9O)3Ti-Co(CO)4] (1a) and shows it to crystallize in the ortho rhombic space group Pbn2(1), with a = 1192.5(7) pm, b = 1375.8(9) pm, c = 1405.0(10) pm, and Z = 4. The variation of the alkoxide ligand lea ds to the more thermally unstable derivatives [(RO)3-TiCo(CO)4] (R = i -C3H7, CH(CF3)2, Ph), whereas trans-[(tC4H9O)3TiCo(CO)3(PPh3)] is form ed in a elective axial carbon monoxide ligand substitution reaction be tween 1a and triphenylphosphine.