The reductive elimination of methyl groups from PtIV is a vital step in Shilov-type selective oxidation of methane to methanol; we report a series of PtII and PtIV aminotroponimate (ATI) complexes that readily interconvert between methyl PtII and dimethyl PtIV species. The complex (ATI)PtII(CH3)(SMe2) readily undergoes oxidative addition of MeX (X = I, OTf) to yield (ATI)PtIV(CH3)2(X)(SMe2).  The X ligand can be exchanged with various Lewis bases to form a series of neutral and cationic species PtIV species which have been characterized by NMR and x-ray crystallography.  Reaction of the PtIV complex with different phosphines leads to the formation of stable PtIV species in some cases and in other cases it leads to reductive elimination to form (ATI)Pt(Me)(L), either with an observable PtIV intermediate or with no observable intermediate. Studies on the mechanism of reductive elimination and its dependence on the nature of the phosphine ligands will be reported.

Reductive elimination from aminotropiminate dimethyl platinum(IV) complexes promoted by sterically hindered lewis bases

244th National Meeting (2012)

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