The development of metal-ligand platforms in a proposed aerobic Shilov-type system involving sequential (i) C-H activation, (ii) Aerobic Oxidation and (iii) C-O Reductive Elimination is of great importance in achieving atom-economical catalytic cycles. While Di(2-pyridyl)dihydrocarbylborate (hydrocarbyl = Me (dmdpb), Ph (dpdpb)) supported Pt(II) complexes can efficiently activate C-H bonds of a number of alkanes and arenes, their oxidation results in the destruction of the anionic borate ligand via B-to-Pt(IV) hydrocarbyl migration and formation of dihydrocarbyl Pt(IV) species inert in C-X reductive elimination. In an attempt to generate in situ a Pt(IV)-monomethyl complex via the B-to-Pt(IV) methyl migration, the oxidation of dpdmb-supported Pt(II) complex bearing no hydrocarbyl groups on the Pt(II)-center, (dmdpb)PtII(SMe2)(OMe), was found to yield a product of C-O reductive elimination quantitatively. In this presentation we describe our efforts in designing and synthesizing novel borate ligands that resist B-to-Pt(IV) hydrocarbyl migration and that support the whole reaction sequence (i)-(iii) above.

Toward completing the aerobic version of the Shilov cycle: C-H activation, aerobic oxidation, and subsequent C-O elimination in Pt complexes supported by novel di(2-pyridyl)dihydrocarbylborato ligands

245th National Meeting (2013)

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