About: A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate

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About: A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate Goto Sponge NotDistinct Permalink

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Description	The bis-bidentate bridging function of gbha2- with N,O/N,O coordination was observed for the first time in the complex (.mu.-gbha)[RuIII(acac)2]2 (1). Density functional theory calculations of 1 yield a triplet ground state with a large (.DELTA.E > 6000 cm-1) singlet-triplet gap. Complex 1 undergoes two one-electron reduction and two one-electron oxidation steps; the five redox forms {(.mu.-gbha)[Ru(acac)2]2}n ( n = -2, -1, 0, +1, +2) were characterized by UV-vis-NIR spectroelectrochemistry. The paramagnetic intermediates were also investigated by electron paramagnetic resonance (EPR) spectroscopy. The monoanion is best described as a 1,4-diazabutadiene radical anion containing ligand gbha•3-, which binds two ruthenium(III) centers. The EPR-active monocation exhibits a broad intervalence charge-transfer band at 1800 nm, indicating a valence-averaged (Ru3.5)2 formulation (class III) with a tendency toward class II (borderline situation). The bis-bidentate bridging function of gbha2- with N,O/N,O coordination was observed for the first time in the complex (.mu.-gbha)[RuIII(acac)2]2 (1). Density functional theory calculations of 1 yield a triplet ground state with a large (.DELTA.E > 6000 cm-1) singlet-triplet gap. Complex 1 undergoes two one-electron reduction and two one-electron oxidation steps; the five redox forms {(.mu.-gbha)[Ru(acac)2]2}n ( n = -2, -1, 0, +1, +2) were characterized by UV-vis-NIR spectroelectrochemistry. The paramagnetic intermediates were also investigated by electron paramagnetic resonance (EPR) spectroscopy. The monoanion is best described as a 1,4-diazabutadiene radical anion containing ligand gbha•3-, which binds two ruthenium(III) centers. The EPR-active monocation exhibits a broad intervalence charge-transfer band at 1800 nm, indicating a valence-averaged (Ru3.5)2 formulation (class III) with a tendency toward class II (borderline situation). (en) Bis-bidentátní můstková funkce aniontu gbha2- s N,O/N,O koordinací byla pozorována poprvé u komplexu (.mu.-gbha)[RuIII(acac)2]2 (1). Z DFT výpočtů 1 vyplývá tripletový základní stav s velkou (.DELTA.E > 6000 cm-1) singlet-triplet diferencí. Komplex 1 podléhá dvěma jednoelektronovým redukcím a dvěma jednoelektronovým oxidačním krokům; pět redox forem{(.mu.-gbha)[Ru(acac)2]2}n ( n = -2, -1, 0, +1, +2 ) bylo charakterizováno UV-VIS-NIR spektroelektrochemií. Paramagnetické intermediáty byly také vyšetřovány elektronovou paramagnetickou resonancí (EPR ). Monoanion je nejlépe popsán jako 1,4-diazabutadienový radikál-aniontový ligand gbha•3-, který váže dvě rutheniová(III) centra. EPR aktivní monokation vzkazuje široký intervalenční pás přenosu náboje u 1800 nm, ukazující na valenčně-zprůměrovanou (Ru3.5)2 formulaci (třída III ) s tendencí k třídě II (hraniční situace). (cs)
Title	A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate Nový koordinační mod u fotometrického činidla glyoxalbis(2-hydroxylanil ) (H2gbha): Bis-bidentátní můstek gbha2- v redox řadě {(.mu.-gbha)[Ru(acac)2]2}n (n =-2,-1, 0,+1,+2), zahrnující radikálem přemostěný dirutheniový(III ) a RuIII/RuIV meziprodukt (cs) A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate (en)
skos:prefLabel	A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate Nový koordinační mod u fotometrického činidla glyoxalbis(2-hydroxylanil ) (H2gbha): Bis-bidentátní můstek gbha2- v redox řadě {(.mu.-gbha)[Ru(acac)2]2}n (n =-2,-1, 0,+1,+2), zahrnující radikálem přemostěný dirutheniový(III ) a RuIII/RuIV meziprodukt (cs) A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate (en)
skos:notation	RIV/61388955:_____/05:00027712!RIV06-AV0-61388955
http://linked.open.../vavai/riv/strany	8715;8722
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(IAA400400505), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	24
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	510937
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/05:00027712
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	spectroelectrochemical properties; oxidation-state; dinuclear ruthenium(III) (en)
http://linked.open.../riv/klicoveSlovo	spectroelectrochemical properties dinuclear ruthenium(III) oxidation-state
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[80A4819390D1]
http://linked.open...i/riv/nazevZdroje	Inorganic Chemistry
http://linked.open...in/vavai/riv/obor	CF
http://linked.open...ichTvurcuVysledku	1 (xsd:int)
http://linked.open...cetTvurcuVysledku	10 (xsd:int)
http://linked.open...vavai/riv/projekt	Redox reactions of free radicals, reactivity in presence of host molecules
http://linked.open...UplatneniVysledku	2005
http://linked.open...v/svazekPeriodika	44
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Jimenez-Aparicio, R. Kaim, W. Lahiri, G. K. Sarkar, B. Urbanos, F. A. Kar, S. Roy, D. Sunoj, R. B. Ghumaan, 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	8 (xsd:int)
is http://linked.open...avai/riv/vysledek of	A new coordination mode of the photometric reagent gilyoxalbis(2-hydroxyanil) (H2gbha): Bis-bidentate bridging by gbha2- in the redox series {(.mu.-gbha)[Ru(acac)2]2}n, including a radical-bridged diruthenium(III) and a RuIII/RuIV intermediate

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