Synthesis, characterization and reactivity of trans-dihydroxy platinum(IV) porphyrins

Abstract

Synthesis of two trans-dihydroxy platinum(IV) porphyrins (TPP, tetraphenylporphyrin and F[Formula: see text]TPP, tetrakispentafluorophenylporphyrin) by dimethyl dioxirane (DMD) oxidation of their Pt[Formula: see text] porphyrin precursors have been described. The oxidation state of Pt cation in such complexes was assessed by X-ray photoelectron spectroscopy and shown to be [Formula: see text]4. More importantly, proton was found to promote the formation and stabilization of the trans-dihydroxy platinum(IV) porphyrins, as revealed by UV-vis spectroscopic results and single crystal structures. In addition, these trans-dihydroxy Pt[Formula: see text] porphyrins were much easier to be reduced than their Pt(II) counterparts and capable to transfer oxygen atom to triphenylphosphine and thioanisol, which is important for further application of Pt(IV) complexes in catalytic reactions.