SYNTHESIS AND PROPERTIES OF SOME NOVEL BIS(CYCLOPENTADIENYL)SILYLTITANIUM(III) COMPLEXES

The complexes Cp2Ti(SiHRR')L [where L = Et3P, R = H, and R' = Ph (5); L = Me3P, R = H (6), Ph (7), and Me (8), and R' = Ph] have been prepared as crystalline solids by the reaction of Cp2TiMe2 with the appropriate silane in the presence of the phosphine ligand. X-ray structures of 5 and 7 were determined. 7 gave a high-quality structure [Rw = 0.030, monoclinic, P21/n, a = 8.743 (1) Å, b = 26.192 (5) Å, c = 10.289 (2) Å, β = 100.97 (1)°, Ti-P = 2.609 (1) Å, Ti-Si = 2.652 (1) Å, Si-Ti-P = 84.8 (1)°]. The structure of 5 was also determined [Rw = 0.050, orthorhombic, P212121, a = 8.312 (4) Å, b = 14.994 (5) Å, c = 17.451 (4) Å], and the refined molecular parameters were indistinguishable from those of 7. All of the compounds are paramagnetic monomers. Their isotropic EPR spectra in toluene were measured. In each case hyperfine coupling of the unpaired electron to 47Ti, 49Ti, 32P, and 1H was resolved. © 1990, American Chemical Society. All rights reserved.