The remarkable catalytic activity of late second- and third-row transition metals arises in large part from their tendency to link bond-making and breaking steps with two-electron changes in oxidation state during a catalytic cycle. Although typically these electron transfers occur by inner-sphere mechanisms, platinum and palladium complexes designed by our group undergo reversible outer-sphere two-electron changes, enabling thermodynamic information about these complexes to be gathered electrochemically. Further analysis of thermodynamic potentials in relation to a series of complexes by cyclic voltammetry, UV-Vis spectroscopy, 1H and 195Pt NMR, and titrations indicate that there is communication between the dangling nucleophiles that is consistent with preorganization of the complex for geometry rearrangement between square planar Pt(II) and octahedral Pt(IV).

Intraligand electronic communication in outer-sphere multi-electron transfer reagents

246th National Meeting (2013)

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