Triazenido ruthenium(II) complexes Ru(bpy)(RNNNR)X R = 2-CF3C6H4, X = BF4 (1-BF4); R = 4-MeOC6H4, X = BF4 (2-BF4), ClO4 (2-ClO4) and Ru(Cym)(NCMe)(RNNNR)SbF6 R = 4-MeOC6H4 (3-SbF6), Cym = cymene were prepd. and the structures of 2-ClO4 and 3-SbF6 were detd. by x-ray crystallog. 1+, 2+ And 3+ all undergo electrochem. reversible oxidns., and ESR spectra of the paramagnetic complexes after 1-electron oxidn. are reported. Spin densities for the oxidized forms were calcd. by DFT methods. The ESR results demonstrating the triazenyl radical ligand character in 32+ and, to a lesser extent, in 2+ are supported by the DFT calcns. Calcns. showed that during oxidn. of 2, a significant part of spin-d. and geometry change involves the N-aryl substituents, indicating non-innocence of the ligand. The corresponding observations are apparently absent for the NO2n ligand system, and reasons for this are discussed. on SciFinder(R)
%0 Journal Article
%1 Ehret.2013
%A Ehret, Fabian
%A Bubrin, Martina
%A Zalis, Stanislav
%A Kaim, Wolfgang.
%D 2013
%J Angewandte Chemie, International Edition
%K DFT ESR;electrochem aryl complex complex;triazenido crystal ligand noninnocence oxidn prepn radical ruthenium structure triazenido triazenyl vs
%N 17
%P 4673--4675
%R 10.1002/anie.201209260
%T Discovering More Non-Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on NO2n as a \dqSuspect\dq Ligand
%V 52
%X Triazenido ruthenium(II) complexes Ru(bpy)(RNNNR)X R = 2-CF3C6H4, X = BF4 (1-BF4); R = 4-MeOC6H4, X = BF4 (2-BF4), ClO4 (2-ClO4) and Ru(Cym)(NCMe)(RNNNR)SbF6 R = 4-MeOC6H4 (3-SbF6), Cym = cymene were prepd. and the structures of 2-ClO4 and 3-SbF6 were detd. by x-ray crystallog. 1+, 2+ And 3+ all undergo electrochem. reversible oxidns., and ESR spectra of the paramagnetic complexes after 1-electron oxidn. are reported. Spin densities for the oxidized forms were calcd. by DFT methods. The ESR results demonstrating the triazenyl radical ligand character in 32+ and, to a lesser extent, in 2+ are supported by the DFT calcns. Calcns. showed that during oxidn. of 2, a significant part of spin-d. and geometry change involves the N-aryl substituents, indicating non-innocence of the ligand. The corresponding observations are apparently absent for the NO2n ligand system, and reasons for this are discussed. on SciFinder(R)
@article{Ehret.2013,
abstract = {Triazenido ruthenium(II) complexes [Ru(bpy)(RNNNR)]X [R = 2-CF3C6H4, X = BF4 (1-BF4); R = 4-MeOC6H4, X = BF4 (2-BF4), ClO4 (2-ClO4)] and [Ru(Cym)(NCMe)(RNNNR)]SbF6 [R = 4-MeOC6H4 (3-SbF6), Cym = cymene] were prepd. and the structures of 2-ClO4 and 3-SbF6 were detd. by x-ray crystallog. 1+, 2+ And 3+ all undergo electrochem. reversible oxidns., and ESR spectra of the paramagnetic complexes after 1-electron oxidn. are reported. Spin densities for the oxidized forms were calcd. by DFT methods. The ESR results demonstrating the triazenyl radical ligand character in 32+ and, to a lesser extent, in 2+ are supported by the DFT calcns. Calcns. showed that during oxidn. of 2, a significant part of spin-d. and geometry change involves the N-aryl substituents, indicating non-innocence of the ligand. The corresponding observations are apparently absent for the [NO2]n ligand system, and reasons for this are discussed. [on SciFinder(R)]},
added-at = {2022-06-15T11:26:56.000+0200},
author = {Ehret, Fabian and Bubrin, Martina and Zalis, Stanislav and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/245c164147f00c302cce32bee060431c9/huebleriac},
doi = {10.1002/anie.201209260},
interhash = {e7ce7152ab2275fc32ce224cad9de66c},
intrahash = {45c164147f00c302cce32bee060431c9},
issn = {1433-7851},
journal = {Angewandte Chemie, International Edition},
keywords = {DFT ESR;electrochem aryl complex complex;triazenido crystal ligand noninnocence oxidn prepn radical ruthenium structure triazenido triazenyl vs},
number = 17,
pages = {4673--4675},
timestamp = {2022-06-15T09:26:56.000+0200},
title = {Discovering More Non-Innocence: Triazenido versus Triazenyl Radical Ligand Function, and a Comment on [NO2]n as a {\dq}Suspect{\dq} Ligand},
volume = 52,
year = 2013
}
