Science of Synthesis

Mikami, K.; Matsumoto, Y.; Shiono, T., Science of Synthesis, (2003) 2, 514.

The carbonyl ligands in [Ti(Cp)2(CO)2] (‌102‌) are photolabile and its photolysis in the presence of an excess of trifluorophosphine results in the formation of [Ti(Cp)2(PF3)2] (‌118‌) via complex ‌117‌ (‌Scheme 61‌).[‌251‌] The monophosphine complex [Ti(Cp)2(CO)(PEt3)] (‌119‌) can be prepared from either photochemical or thermal reactions of [Ti(Cp)2(CO)2] (‌102‌) and triethylphosphine in hydrocarbon solvents.[‌251‌] [Ti(Cp)2(CO)(PPh3)] is accessible by thermal reaction of [Ti(Cp)2(CO)2] (‌102‌) with triphenylphosphine.[‌251‌] The phosphine ligands of the monophosphine complexes are very labile in solution. For example, reactions of [Ti(Cp)2(CO)(PEt3)] (‌119‌) with trifluorophosphine, triphenyl phosphite, and diphenylacetylene lead to [Ti(Cp)2(CO)(PF3)] (‌117‌), [Ti(Cp)2(CO){P(OPh)3}] (‌121‌), or [Ti(Cp)2(CO)(PhC≡CPh)] (‌120‌, Ar1 = Ph), respectively (‌Scheme 61‌).[‌251‌] The kinetics of the carbonyl substitution reactions of [Ti(Cp)2(CO)2] (‌102‌) with phosphines have been studied.[‌252‌]

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References

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• 8.Meeeee-Meee, (8888) M 88-8, 88.