Abstract
A five coordinate paramagnetic fluorotitanium(III) tetraphenylporphyrin complex, TiF(TPP), was prepared by zinc amalgam reduction of the corresponding difluorotitanium(IV) complex. The benzenethiolatotitanium(III) analog, Ti(SC6H5)(TPP), was obtained by metathesis with sodium benzenethiolate. Both complexes exhibit the features that are essential for dioxygen adduct formation, and indeed, they undergo fast autoxidation in the presence of dioxygen. Autoxidation mechanisms are proposed on the basis of the observed oxidation end-products and of the ability of the coordinated benzenethiolate to act as a one-electron reductant. Implication on the function of the axial thiolate ligand during cytochrome P-450 catalytic cycle is presented.
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