Thermal and photochemical olefin isomerizations with complex as initiator

Article abstract of DOI:10.1016/0022-328X(87)80235-8

Irradiation of the complex <(C5Me4H)2Ti(CH3)2> in an olefin as a solvent promotes stereospecific photoassisted isomerizations: olefins with terminal double bonds are rapidly isomerized into 2-alkenes with an E-configuration.Kinetic studies of hydrogen migrations and of Z-E isomerizations of disubstituted olefins have demonstrated the influence of substitution and of branching of the hydrocarbon chain on the course of the reaction.Formation of paramagnetic complexes of Ti^III that are probably intermediates in these reactions has been confirmed by ESR.The same reactions, but with a lower stereoselectivity, are initiated thermally by the <(C5Me4H)2Ti(CH3)2> complex.