EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k
A survey of 18 paramagnetic species [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, phosphanes, carbonyl, cyclopentadienides,...
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2004
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14341948_v_n14_p2902_Frantz http://hdl.handle.net/20.500.12110/paper_14341948_v_n14_p2902_Frantz |
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paper:paper_14341948_v_n14_p2902_Frantz2023-06-08T16:14:28Z EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k Density functional calculations EPR spectroscopy Nitric oxide Radical complexes Ruthenium amine carbonyl derivative cyanide cyclopentadiene derivative halide hydroxide imine ligand metal nitric oxide nitrile nitrogen organometallic compound oxygen pyridine ruthenium thiocyanate analytic method article calculation complex formation electrolysis electron spin resonance magnetism nitrosylation A survey of 18 paramagnetic species [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, phosphanes, carbonyl, cyclopentadienides, halides, hydride, hydroxide, thiocyanate or cyanide: g 1 = 2.015 ± 0.02, g2 = 1.990 ± 0.015, g 3 = 1.892 ± 0.03, gav = 1.968 ± 0.02, Δg = g1 - g3 = 0.122 ± 0.037, A 2(14N) = 3.3 ± 0.5 mT. This rather small variability, smaller still if the organometallic compounds 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 calculations were employed for [(NC)5Ru(NO)]3-to reproduce the EPR data, to evaluate the spin distribution (58% spin density on NO), and to reveal structural changes on reduction such as the Ru-N-O bending and Ru-NO bond lengthening. In addition, the possibility of staggered and eclipsed conformations is discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004. 2004 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14341948_v_n14_p2902_Frantz http://hdl.handle.net/20.500.12110/paper_14341948_v_n14_p2902_Frantz |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Density functional calculations EPR spectroscopy Nitric oxide Radical complexes Ruthenium amine carbonyl derivative cyanide cyclopentadiene derivative halide hydroxide imine ligand metal nitric oxide nitrile nitrogen organometallic compound oxygen pyridine ruthenium thiocyanate analytic method article calculation complex formation electrolysis electron spin resonance magnetism nitrosylation |
| spellingShingle |
Density functional calculations EPR spectroscopy Nitric oxide Radical complexes Ruthenium amine carbonyl derivative cyanide cyclopentadiene derivative halide hydroxide imine ligand metal nitric oxide nitrile nitrogen organometallic compound oxygen pyridine ruthenium thiocyanate analytic method article calculation complex formation electrolysis electron spin resonance magnetism nitrosylation EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| topic_facet |
Density functional calculations EPR spectroscopy Nitric oxide Radical complexes Ruthenium amine carbonyl derivative cyanide cyclopentadiene derivative halide hydroxide imine ligand metal nitric oxide nitrile nitrogen organometallic compound oxygen pyridine ruthenium thiocyanate analytic method article calculation complex formation electrolysis electron spin resonance magnetism nitrosylation |
| description |
A survey of 18 paramagnetic species [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, phosphanes, carbonyl, cyclopentadienides, halides, hydride, hydroxide, thiocyanate or cyanide: g 1 = 2.015 ± 0.02, g2 = 1.990 ± 0.015, g 3 = 1.892 ± 0.03, gav = 1.968 ± 0.02, Δg = g1 - g3 = 0.122 ± 0.037, A 2(14N) = 3.3 ± 0.5 mT. This rather small variability, smaller still if the organometallic compounds 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 calculations were employed for [(NC)5Ru(NO)]3-to reproduce the EPR data, to evaluate the spin distribution (58% spin density on NO), and to reveal structural changes on reduction such as the Ru-N-O bending and Ru-NO bond lengthening. In addition, the possibility of staggered and eclipsed conformations is discussed. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004. |
| title |
EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| title_short |
EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| title_full |
EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| title_fullStr |
EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| title_full_unstemmed |
EPR insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [LnRuII-NO.]k |
| title_sort |
epr insensitivity of the metal-nitrosyl spin-bearing moiety in complexes [lnruii-no.]k |
| publishDate |
2004 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14341948_v_n14_p2902_Frantz http://hdl.handle.net/20.500.12110/paper_14341948_v_n14_p2902_Frantz |
| _version_ |
1768546738295013376 |