Activation of Homolytic Si-Zn and Si-Hg Bond Cleavage, Mediated by a Pt-0 Complex, via Novel Pt-Zn and Pt-Hg Compounds

摘要

The thermally stable [(tBuMe(2)Si)(2)M] (M = Zn, Hg) generate R3Si center dot radicals in the presence of [(dmpe)Pt(PEt3)(2)] at 60-80 degrees C. The reaction proceeds via hexacoordinate Pt complexes, (M = Zn (2a and 2b), M = Hg (3a and 3b)) which were isolated and characterized. Mild warming or photolysis of 2 or 3 lead to homolytic dissociation of the Pt-MSiR3 bond generating silyl radicals and novel unstable pentacoordinate platinum paramagnetic complexes (M = Zn (5), Hg (6)) whose structures were determined by EPR spectroscopy and DFT calculations.