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2.10.3.2.1 Variation 1: Transmetalation between Magnesium Cyclopentadienide Salts and ­Titanium(III) Chloride

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032477.

The synthesis of dihalobis(η5-cyclopentadienyl)titanium(IV) and trihalo(η5-cyclopenta­dien­yl)titanium(IV) complexes by reaction of magnesium bis(cyclopentadienide) complexes with titanium(IV) chloride was reported in 1959.[‌129‌] Brintzinger has reported the syntheses of tetramethylethylene-bridged disubstituted titanocene derivatives 59 (R1=H, t-Bu, TMS, iPr, CMe2Ph, 1-phenylcyclohexyl). These compounds are formed by reductive coupling of the appropriate 6,6-dimethylpentafulvene derivatives with magnesium in carbon tetrachloride and reaction of the resulting dimagnesium compounds with the titanium(III) chloridetris(tetrahydrofuran) complex (Scheme 22).[‌130‌,‌131‌] The substituted complexes are obtained as meso- and rac-isomers.

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