Reaction of [Mn(OAc)(TPP)] (TPP = dianion of meso-tetraphenylporphine) with both HSSi i Pr 3 and HSSiPh 3 in the presence of air leads to formation of the corresponding siloxide complexes, [Mn(OSiR 3 )(TPP)] (R = i Pr 3 , Ph), via silyl group transfer from S to O. The new compounds have been fully characterized in solution and the solid state and represent rare examples of Mn(III) porphyrinates containing Lewis basic axial ligands. X-ray crystallographic analyses of both complexes reveal very short Mn-O bond distances consistent with the presence of a siloxide ligand. Investigations of the reaction pathway are consistent with initial reduction of [Mn(OAc)(TPP)] to [Mn II (TPP)] by the silanethiol. Subsequent aerobic oxidation of the reaction mixture is proposed to generate a Mn(III) porphyrinate and the corresponding silanol, which combine to yield the observed siloxide complex. These findings stand in sharp contrast to those of iron(III) porphyrinates, where silanethiolate complexes are stable.
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