Synthesis,crystal structure and reaction of differentially ring-substituted titanocene dichlorides

Summary A new class of differentially ring-substituted titanocene dichlorides of the type CpCpTiCl₂ has been prepared by reacting CpM (M=Li, K; Cp=RC₅H₄) with CpTiCl₃ (Cp=MeOCH₂CH₂C₅H₄). The crystal structure of Cp(PhCEt₂C₅H₄)TiCl₂, the first example, has been determined by x-ray diffraction and refined to a final R factor of 0.0532 for 2304 reflections. The crystal belongs to the monoclinic space group C _2h ⁵ –P2₁/c with unit cell parameters:a 10.205(6),b 13.003(5),c 17.591(9) Å, 101.91(4)°, V=2284 ų, Z=4 and Dc=1.32 g/cm^–3. Replacement of one neomenthyl in bis(neomenthyl-cyclopentadienyl)titanium dichloride by one MeOCH₂CH₂ — raises the e.e. value from 5.8% to 11.2% in the catalytic asymmetric hydrogenation of 2-phenyl-1-butene.