Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 534.

(η4-Buta-1,3-diene)(η5-cyclopentadienyl)(η3-1-methylallyl)titanium(II) is isolated from the reaction of trichloro(η5-cyclopentadienyl)titanium(IV) (‌79‌) with 3 equivalents of crotylmagnesium bromide; the reaction proceeds by proton abstraction from one of the 1-methylallyl ligands in the (η5-cyclopentadienyl)tris(η3-1-methylallyl)titanium(IV) intermediate.[‌300‌,‌301‌] The reaction of [Ti(Cp*)Cl3] (‌6‌) with 3 equivalents of 1-methylallylmagnesium bromide affords the brown (η4-buta-1,3-diene)(η3-1-methylallyl)(η5-pentamethylcyclopentadienyl)titanium(II) complex in 30% yield.[‌302‌] This complex can be used to prepare (η4-buta-1,3-diene)(chloro)(η5-pentamethylcyclopentadienyl)titanium(II) by comproportionation with [Ti(Cp*)Cl3] (‌6‌).[‌296‌]

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