Mechanistic insight into rapid oxygen-atom transfer from a calix-functionalized polyoxovanadate

Abstract

We report accelerated rates of oxygen-atom transfer from a polyoxovanadate–alkoxide cluster following functionalization with a 4-tertbutylcalix[4]arene ligand. Incorporation of this electron withdrawing ligand modifies the electronics of the metal oxide core, favoring a mechanism in which the rate of oxygen-atom transfer is limited by outer-sphere electron transfer.