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)
%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*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)
@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 = {2019-07-15T13:41:23.000+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/b_schwederski},
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 = {2019-07-15T11:42:10.000+0200},
title = {Reversible Intramolecular Single-Electron Oxidative Addition Involving a Hemilabile Noninnocent Ligand},
volume = 30,
year = 2011
}