Synthesis of 1-Methyl-3-aryl-substituted Titanocene and Zirconocene Dichlorides and Crystal Structure of Bis[η⁵-1-methyl-3-(α, α-dimethylbenzyl) cyclopentadienyl] titanium Dichloride

The syntheses of a series of l-methyl-3-aryl-substituted titanocene and zirconocene dichlorides are reported. These complexes are synthesized by the reaction of 2- and 3-methyl-6, 6-dimethylfulvenes (1:4) with aryllithium, followed by the reaction with TiCl₄·2THF, ZrCl₄ and (CpTiCl₂)₂O respectively, to give complexes 1–5. The complex [η⁵-1-methyl-3-(α, α-dimethylbenzyl) cyclopentadienyl] titanium dichloride has been studied by X-ray diffraction. The red crystal of this complex is monoclinic, space group P2_t/C with unit cell parameters: a =6.973(6) × 10⁻¹ nm, b =36.91(2) × 10⁻¹ nm, c = 10.063(4) × 10⁻¹ nm, α=β= γ = 93.35(5)°, V = 2584(5) × 10⁻³ nm³ and Z = 4. Refinement for 1004 observed reflections gives the final R of 0.088. There are four independent molecules per unit cell.