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2.10.7 Product Subclass 7: Titanium–Allyl, –Allenyl, and –Propargyl Complexes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032518.

Review articles are available on the syntheses and reactivities of titaniumallyl, allenyl, and propargyl complexes.[‌13‌] Monomeric [Ti(Cp)2(η3-allyl)] complexes have been prepared by the following three methods:[‌256‌] (1) Reaction of an allyl Grignard reagent with [{Ti(Cp)2Cl}2] (92); (2) Reaction of 2 equivalents of an allyl Grignard reagent with [Ti(Cp)2Cl2] (78); (3) Reduction of [Ti(Cp)2Cl2] (78) with 2 equivalents of propylmagnesium chloride in the presence of a 1,3-diene. In method 2, 1 equivalent of allyl Grignard reagent acts as a reducing reagent to give a titanium(III) complex from the titanium(IV) complex. All the allyl complexes were found to be purple or violet crystalline solids with magnetic moments near to the spin-only value. An X-ray crystallographic investigation of the 1,2-dimethylallyl complex [Ti(Cp)2(η3-1,2-dimethylallyl)] showed it to be monomeric with a π-bonded allyl group.[‌257‌]

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