Treatment of the well-defined complexes (TTP)Ti(η2-EtC⋮CEt) or trans-(TTP)Ti(THF)2 with vicinal dichloroalkanes or dichloroalkenes results in the production of alkenes or alkynes and 2 equiv of (TTP)TiCl. This net two-electron redox reaction arises from two formal one-electron reduction processes mediated by chlorine atom transfer. Oxygen atom transfer occurs when the Ti(II) porphyrins are treated with several different sulfoxides or epoxides, resulting in two-electron redox products, (TTP)TiO, the sulfide or alkene, and EtC⋮CEt or THF. The electronic properties of the substituents on the sulfoxides or epoxides correlate with the yield and rate of the deoxygenation reactions.
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