Early-late transition metal bonds: Ruthenium-titanium compounds with aryloxide ligands

Article abstract of DOI:10.1021/om00111a010

[RuH(CO)₂(Cp)] reacts with [Ti(2,6-Me₂C₆H₃O)(NMe₂)₃] (1) and [Ti(2,6-Me₂C₆H₃O)₂(NMe ₂)₂] (2) to produce [(NMe₂)₂(2,6-Me₂C₆H ₃O)TiRu(CO)₂(Cp)] (3) and [(NMe₂)(2,6-Me₂C₆H₃O) ₂TiRu(CO)₂(Cp)] (4), respectively. Both products were characterized spectroscopically, and the structure of 4 was determined by an X-ray diffraction study. Compound 4 crystallizes in the space group P2₁/n with a = 8201 (3) ? b = 18.776 (4) ?, c = 16.739 (6) ?, β = 103.90 (3)°, and V = 2526.29 ?³. Full-matrix least-squares refinement converged at R = 5.6% and R_w = 6.5%. There is a direct, unbridged bond between titanium and ruthenium in 4, with a metal-metal bond length of 2.573 (1) ?. Despite steric crowding in 4, this Ru-Ti distance is 0.09 ? shorter than the Ru-Ti distance in [(NMe₂)₃TiRu(CO)₂(Cp)], attributed in part to the weaker electron-donor ability of aryloxides.