About: The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1)

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About: The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1) Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	The complexes [M(bpy)2(Q)](PF6) were isolated and studied by X and W band EPR at ambient temperatures and in frozen dichloromethane solution at 4 K. For M = Ru the 14N hyperfine splitting confirms the RuII/semiquinone formulation although at a > 1 mT the 99,101Ru satellite coupling is unusually high. W band EPR allowed us to determine the relatively small g anisotropy .DELTA.g = g1-g3 = 0.0665 for the ruthenium complex. The osmium analogue exhibits a much higher difference .DELTA.g = 0.370 which is attributed not only to the larger spin-orbit coupling constant but also to a higher extent of metal contribution to the singly occupied MO. The difference .DELTA.E between oxidation and reduction potentials of the radical complexes is larger for the ruthenium compound (.DELTA.E = 0.92 V) than for the osmium analogue (.DELTA.E = 0.76), confirming the difference in metal/ligand interaction. The complexes [M(bpy)2(Q)](PF6) were isolated and studied by X and W band EPR at ambient temperatures and in frozen dichloromethane solution at 4 K. For M = Ru the 14N hyperfine splitting confirms the RuII/semiquinone formulation although at a > 1 mT the 99,101Ru satellite coupling is unusually high. W band EPR allowed us to determine the relatively small g anisotropy .DELTA.g = g1-g3 = 0.0665 for the ruthenium complex. The osmium analogue exhibits a much higher difference .DELTA.g = 0.370 which is attributed not only to the larger spin-orbit coupling constant but also to a higher extent of metal contribution to the singly occupied MO. The difference .DELTA.E between oxidation and reduction potentials of the radical complexes is larger for the ruthenium compound (.DELTA.E = 0.92 V) than for the osmium analogue (.DELTA.E = 0.76), confirming the difference in metal/ligand interaction. (en) Komplexy [M(bpy)2(Q)](PF6) byly izolovány a studovány pomocí X- a W-band EPR za normální teploty a v zmrzlém dichloromethanovém roztoku při 4 K. Pro M = Ru, 14N hyperjemné štěpení potvrzuje formulaci RuII/semichinon, ačkoli při a > 1 mT je spojení vlivem 99,101Ru neobvykle vysoké. W-band EPR umožnila určit relativně malou g anisotropii .DELTA.g = g1-g3 = 0.0665 pro rutheniový komplex. Osmiový analog vykazuje mnohem vyšší rozdíl .DELTA.g = 0.370 který je připsán ne pouze větší konstantě spin-orbitálního spojení, ale také vyššímu podílu příspěvku kovu k MO obsazenému jedním elektronem. Rozdíl .DELTA.E mezi oxidačními a redukčnimi potenciály radikálových komplexů je větší pro rutheniovou sloučeninu (.DELTA.E = 0.92 V ) než pro osmiový analog (.DELTA.E = 0.76), což potvrzuje rozdíl v metal/ligand interakci. Elektrochemicky generované stavy [M(bpy)2(Q )]n+, n = 0,1,2, byly také charakterizovány s použitím UV-VIS-NIR spektroelektrochemie. (cs)
Title	The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1) The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1) (en) Redox série [M(bpy)2(Q )]n+, M = Ru nebo Os, Q = 3,5-Di-tert-butyl-N-fenyl-1,2-benzochinonmonoimin. Izolace a kompletní X- a W- band EPR studie semichinonových stavů (n = 1) (cs)
skos:prefLabel	The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1) The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1) (en) Redox série [M(bpy)2(Q )]n+, M = Ru nebo Os, Q = 3,5-Di-tert-butyl-N-fenyl-1,2-benzochinonmonoimin. Izolace a kompletní X- a W- band EPR studie semichinonových stavů (n = 1) (cs)
skos:notation	RIV/61388955:_____/05:00022081!RIV06-AV0-61388955
http://linked.open.../vavai/riv/strany	2843;2847
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(GA203/03/0821), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	8
http://linked.open...vai/riv/dodaniDat	2006
http://linked.open...aciTvurceVysledku	Fiedler, Jan
http://linked.open.../riv/druhVysledku	J - Článek v odborném periodiku
http://linked.open...iv/duvernostUdaju	S - Úplné a pravdivé údaje nepodléhající ochraně podle zvláštních právních předpisů
http://linked.open...titaPredkladatele	Ústav fyzikální chemie J. Heyrovského AV ČR, v.v.i.
http://linked.open...dnocenehoVysledku	540384
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/05:00022081
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	transition-metal complexes; electrochemistry; ruthenium complexes (en)
http://linked.open.../riv/klicoveSlovo	electrochemistry ruthenium complexes transition-metal complexes
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[5AD4E55AEA05]
http://linked.open...i/riv/nazevZdroje	Inorganic Chemistry
http://linked.open...in/vavai/riv/obor	CG
http://linked.open...ichTvurcuVysledku	1 (xsd:int)
http://linked.open...cetTvurcuVysledku	5 (xsd:int)
http://linked.open...vavai/riv/projekt	Electron transfer to new supramolecular complexes, large molecules with multiple active centers and ordered structures
http://linked.open...UplatneniVysledku	2005
http://linked.open...v/svazekPeriodika	44
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Kaim, W. Sarkar, B. Duboc, C. Ye, S.
http://linked.open...n/vavai/riv/zamer	Struktura, reaktivita a dynamika molekulárních a biomolekulárních systémů: teorie, experiment, aplikace
issn	0020-1669
number of pages	5 (xsd:int)
is http://linked.open...avai/riv/vysledek of	The Redox Series [M(bpy)2(Q)]n+, M = Ru or Os, Q = 3,5-Di-tert-butyl-N-phenyl-1,2-benzoquinonemonoimine. Isolation and a Complete X and W Band EPR Study of the Semiquinone States (n = 1)

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