Synthesis of 1‐Methyl‐3‐aryl‐substituted Titanocene and Zirconocene Dichlorides and Crystal Structure of Bis[η 5 ‐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 TiCl 4 ·2THF, ZrCl 4 and (CpTiCl 2 ) 2 O respectively, to give complexes 1–5. The complex [η 5 ‐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 P 2 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 nm 3 and Z = 4. Refinement for 1004 observed reflections gives the final R of 0.088. There are four independent molecules per unit cell.