Nine derivs. of M(L2-)(p-cymene) (M = Ru, Os, L2- = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepd. and structurally characterized (Ru complexes) as coordinatively unsatd., formally 16 valence electron species. On L2--ligand based oxidn. to EPR-active iminosemiquinone radical complexes, the compds. seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochem. at ambient and low temps. in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the ligand as the main electron transfer site and the metal with fractional (d) oxidn. as the center for redox-activated coordination. Attempts to crystallize Ru(Cym)(QSMe)(PF6) (QSMe = 4,6-di-tert-butyl-2-(2-methylthiophenyl)amidophenolate) produced single crystals of RuIII(QSMe.bul.-)2(PF6) after apparent dissocn. of the arene ligand. on SciFinder(R)
%0 Journal Article
%1 Bubrin.2014
%A Bubrin, Martina
%A Schweinfurth, David
%A Ehret, Fabian
%A Zalis, Stanislav
%A Kvapilova, Hana
%A Fiedler, Jan
%A Zeng, Qiang
%A Hartl, Frantisek
%A Kaim, Wolfgang.
%D 2014
%J Organometallics
%K EPR FMO;mol FMO;ruthenium amidophenolate arene crystal electrochem hemilabile osmium prepn redox ruthenium spectroelectrochem structure
%N 18
%P 4973--4985
%R 10.1021/om5002815
%T Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands
%V 33
%X Nine derivs. of M(L2-)(p-cymene) (M = Ru, Os, L2- = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepd. and structurally characterized (Ru complexes) as coordinatively unsatd., formally 16 valence electron species. On L2--ligand based oxidn. to EPR-active iminosemiquinone radical complexes, the compds. seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochem. at ambient and low temps. in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the ligand as the main electron transfer site and the metal with fractional (d) oxidn. as the center for redox-activated coordination. Attempts to crystallize Ru(Cym)(QSMe)(PF6) (QSMe = 4,6-di-tert-butyl-2-(2-methylthiophenyl)amidophenolate) produced single crystals of RuIII(QSMe.bul.-)2(PF6) after apparent dissocn. of the arene ligand. on SciFinder(R)
@article{Bubrin.2014,
abstract = {Nine derivs. of [M(L2-)(p-cymene)] (M = Ru, Os, L2- = 4,6-di-tert-butyl-N-aryl-o-amidophenolate) were prepd. and structurally characterized (Ru complexes) as coordinatively unsatd., formally 16 valence electron species. On L2--ligand based oxidn. to EPR-active iminosemiquinone radical complexes, the compds. seek to bind a donor atom (if available) from the N-aryl substituent, as structurally certified for thioether and selenoether functions, or from the donor solvent. Simulated cyclic voltammograms and spectroelectrochem. at ambient and low temps. in combination with DFT results confirm a square scheme behavior (ECEC mechanism) involving the ligand as the main electron transfer site and the metal with fractional (\textgreek{d}) oxidn. as the center for redox-activated coordination. Attempts to crystallize [Ru(Cym)(QSMe)](PF6) (QSMe = 4,6-di-tert-butyl-2-(2-methylthiophenyl)amidophenolate) produced single crystals of [RuIII(QSMe.bul.-)2](PF6) after apparent dissocn. of the arene ligand. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Bubrin, Martina and Schweinfurth, David and Ehret, Fabian and Zalis, Stanislav and Kvapilova, Hana and Fiedler, Jan and Zeng, Qiang and Hartl, Frantisek and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2835cae80db788a0a68cd3c2904b7b42f/huebleriac},
doi = {10.1021/om5002815},
interhash = {0537377708466f06dd365f32b7068b74},
intrahash = {835cae80db788a0a68cd3c2904b7b42f},
issn = {0276-7333},
journal = {Organometallics},
keywords = {EPR FMO;mol FMO;ruthenium amidophenolate arene crystal electrochem hemilabile osmium prepn redox ruthenium spectroelectrochem structure},
number = 18,
pages = {4973--4985},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Structure and Spectroelectrochemical Response of Arene-Ruthenium and Arene-Osmium Complexes with Potentially Hemilabile Noninnocent Ligands},
volume = 33,
year = 2014
}