Zusammenfassung
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*Q]0/+ (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)]
Nutzer
