%0 Journal Article %1 Frantz.2004c %A Frantz, Stephanie %A Sarkar, Biprajit %A Sieger, Monika %A Kaim, Wolfgang %A Roncaroli, Federico %A Olabe, Jose A. %A Zalis, Stanislav. %D 2004 %J European Journal of Inorganic Chemistry %K EPR bipyrazine bipyridine nitrosyl prepn pyridine radical ruthenium terpyridine %N 14 %P 2902--2907 %R 10.1002/ejic.200400042 %T EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.bul.]k %X A survey of 18 paramagnetic [LnRu(NO)]k, including seven new examples studied by in situ electrolysis, reveals a surprisingly narrow range of EPR parameters despite a wide variety of ligands such as pyridine, polypyridines, imines, amines, nitriles, phosphines, carbonyl, cyclopentadienides, halides, hydride, hydroxide, thiocyanate or cyanide: g1 = 2.015 $\pm$ 0.02, g2 = 1.990 $\pm$ 0.015, g3 = 1.892 $\pm$ 0.03, gav = 1.968 $\pm$ 0.02, Dg = g1 - g3 = 0.122 $\pm$ 0.037, A2(14N) = 3.3 $\pm$ 0.5 mT. This rather small variability, smaller still if the organometallic compds. are excluded, differs from the wider range of EPR data reported for nitrosyliron species with S = 1/2; apparently, the RuNO7 configuration involves a rather invariant and relatively covalent metal-NO interaction. DFT calcns. were employed for [(NC)5Ru(NO)]3- to reproduce the EPR data, to evaluate the spin distribution (58\% spin d. on NO), and to reveal structural changes on redn. such as the Ru-N-O bending and Ru-NO bond lengthening. The possibility of staggered and eclipsed conformations is discussed. [on SciFinder(R)]

@article{Frantz.2004c, abstract = {A survey of 18 paramagnetic [LnRu(NO)]k, including seven new examples studied by in situ electrolysis, reveals a surprisingly narrow range of EPR parameters despite a wide variety of ligands such as pyridine, polypyridines, imines, amines, nitriles, phosphines, carbonyl, cyclopentadienides, halides, hydride, hydroxide, thiocyanate or cyanide: g1 = 2.015 $\pm$ 0.02, g2 = 1.990 $\pm$ 0.015, g3 = 1.892 $\pm$ 0.03, gav = 1.968 $\pm$ 0.02, \textgreek{D}g = g1 - g3 = 0.122 $\pm$ 0.037, A2(14N) = 3.3 $\pm$ 0.5 mT. This rather small variability, smaller still if the organometallic compds. are excluded, differs from the wider range of EPR data reported for nitrosyliron species with S = 1/2; apparently, the {RuNO}7 configuration involves a rather invariant and relatively covalent metal-NO interaction. DFT calcns. were employed for [(NC)5Ru(NO)]3- to reproduce the EPR data, to evaluate the spin distribution (58{\%} spin d. on NO), and to reveal structural changes on redn. such as the Ru-N-O bending and Ru-NO bond lengthening. The possibility of staggered and eclipsed conformations is discussed. [on SciFinder(R)]}, added-at = {2022-06-15T11:26:56.000+0200}, author = {Frantz, Stephanie and Sarkar, Biprajit and Sieger, Monika and Kaim, Wolfgang and Roncaroli, Federico and Olabe, Jose A. and Zalis, Stanislav.}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e4f9ffd6c988d34ff8c1162d9c438968/huebleriac}, doi = {10.1002/ejic.200400042}, interhash = {173a0951abcf65f96200c98d0d123330}, intrahash = {e4f9ffd6c988d34ff8c1162d9c438968}, issn = {1434-1948}, journal = {European Journal of Inorganic Chemistry}, keywords = {EPR bipyrazine bipyridine nitrosyl prepn pyridine radical ruthenium terpyridine}, number = 14, pages = {2902--2907}, timestamp = {2022-06-15T09:26:56.000+0200}, title = {EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.bul.]k}, year = 2004 }