Abstract
Using the noninnocent ligand Q Q = 4,6-di-tert-butyl-(2-methylthiophenylimino)-o-benzoquinone with a thioether group as potential coordination function, it was possible to substantiate a single-electron transfer induced oxidative addn. within IrCp*Q0/+ (Cp* = C5Me5) via structural characterization (catecholato $\rightarrow$ semiquinonato transition coupled with reversible S$\rightarrow$Ir coordination), via cyclic voltammetry, EPR, and DFT (semiquinone formulation with $\sim$8\% Ir participation). The intramol. rearrangement of the 16-electron precursor IrCp*Q triggered by electron removal illuminates the complementary activities of the substrate binding metal and the electron-buffering ligand as was recently employed by Ringenberg et al. in dihydrogen activation (Organometallics 2010, 29, 1956). on SciFinder(R)
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