0101137 - UFCH-W 20040147 RIV DE eng J - Journal Article
Frantz, S. - Sarkar, B. - Sieger, M. - Kaim, W. - Roncaroli, F. - Olabe, J. A. - Záliš, Stanislav
EPR Insensitivity of the Metal-Nitrosyl Spin-Bearing Moiety in Complexes [Ln RuII-NO.DEG.]k.
[EPR necitlivost části nesoucí spin kov - nitrosyl v komplexech [Ln RuII-NO]k.]
European Journal of Inorganic Chemistry. -, č. 14 (2004), s. 2902-2907. ISSN 1434-1948. E-ISSN 1099-0682
R&D Projects: GA MŠMT OC D14.20
Institutional research plan: CEZ:AV0Z4040901
Keywords : density functional calculations * EPR spectroscopy * nitric oxide
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 2.336, year: 2004

A survey of 18 paramagnetic species [LnRu(NO)]k, including 7 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 ±0.02, g2 = 1.990 ±0.015, g3 = 1.892 ±0.03, gav = 1.968 ±0.02, .DELTA.g = g1-g3 = 0.122 ±0.037, A2(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 (S=1/2)-nitrosyliron species; 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).

Studovaných 18 paramagnetických komplexů [LnRu(NO)]k, včetně 7 nových příkladů studovaných elektrolyticky in situ, vykazuje překvapivě úzkou oblast EPR parametrů pro širokou oblast ligandů jako pyridin, polypyridiny, iminy, aminy, nitrily, fosfiny, karbonyly, cyclopentadienily, halidy, hydridy, hydroxidy, thiokyanaty a kyanid: g1 = 2.015 ±0.02, g2 = 1.990 ±0.015, g3 = 1.892 ±0.03, gav = 1.968 ±0.02, .DELTA.g = g1-g3 = 0.122 ±0.037, A2(14N) = 3.3 ±0.5 mT. Provedené DFT výpočty zreprodukovaly EPR data, ukázaly na rozložení spinové hustoty (58% spinové hustoty na NO), a objasnily strukturní změny v průběhu redukce jako jsou prohnutí Ru-N-O a prodloužení vazby Ru-NO.
Permanent Link: http://hdl.handle.net/11104/0008595