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Please login to access the full content or check if you have access via Method 7: Titanium(II)–Phosphine Complexes by Photolysis of Dicarbonylbis(η5-cyclopentadienyl)titanium(II)

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032514.

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)(PhCCPh)] (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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