%0 Journal Article %1 Huebner.2011 %A Huebner, Ralph %A Weber, Sebastian %A Strobel, Sabine %A Sarkar, Biprajit %A Zalis, Stanislav %A Kaim, Wolfgang. %D 2011 %J Organometallics %K DFT;mol DFT;optimized ESR crystal cyclopentadienyl electrochem iridium methylthiophenyliminosemiquinonate mol prepn spectroelectrochem structure voltammetry %N 6 %P 1414--1418 %R 10.1021/om100969q %T Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand %V 30 %X 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)]

@article{Huebner.2011, 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*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)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Huebner, Ralph and Weber, Sebastian and Strobel, Sabine and Sarkar, Biprajit and Zalis, Stanislav and Kaim, Wolfgang.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/273b4a84a3e8cd372a014af4c1db8fed3/huebleriac}, doi = {10.1021/om100969q}, interhash = {5c78348e274cce4992619d275c3f58b6}, intrahash = {73b4a84a3e8cd372a014af4c1db8fed3}, issn = {0276-7333}, journal = {Organometallics}, keywords = {DFT;mol DFT;optimized ESR crystal cyclopentadienyl electrochem iridium methylthiophenyliminosemiquinonate mol prepn spectroelectrochem structure voltammetry}, number = 6, pages = {1414--1418}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand}, volume = 30, year = 2011 }