About: Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system

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About: Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system Goto Sponge NotDistinct Permalink

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Description	Reakce 3,6-diaryl-1,2,4,5-tetrazinů (aryl = R = phenyl, 2-furyl or 2-thienyl) s 2 equivalenty Ru(acac)(2)(CH3-CN)(2) způsobuje reduktivní otevření tetrazinového kruhu a poskytuje dirutheniové komplexy [(acac)(2)Ru-III(dih-R2-)Ru-III(acac)(2)] s novými můstkovými ligandy 1,2-diiminohydrazido(2-) (dih-R2- = HNC(R)NNC(R)NH2-). Komplexy podléhají dvěma reverzibilním a dobře odděleným jednoelektronovým redukčním a oxidačním procesům. EPR spectroskopie paramagnetických intermediátů s komproporcionačními konstantami K-c > 10(12) a UV-vis-NIR spektroelektrochemie byla použita pro identifikaci dostupných redox stavů, jimiž jsou [(acac)(2)Ru-II(dih-R2-)Ru-II(acac)(2)](2-), [(acac)(2)Ru-II(dih-Rcenter dot-)Ru-II(acac)(2)](-), [(acac)(2)Ru-II(dih-R2-)Ru-III(acac)(2)], [(acac)(2)Ru-III(dih-Rcenter dot-)Ru-III(acac)(2)](+), a [(acac)(2)Ru-III(dih-R)Ru-III(acac)(2)](2+). (cs) Reaction of 3,6-diaryl-1,2,4,5-tetrazines (aryl = R = phenyl, 2-furyl or 2-thienyl) with 2 equiv of Ru(acac)(2)(CH3-CN)(2) results in reductive tetrazine ring opening to yield diruthenium complexes [(acac)(2)Ru-III(dih-R2-)Ru-III(acac)(2)] bridged by the new 1,2-diiminohydrazido(2-) (dih-R2- = HNC(R)NNC(R)NH2-) ligands. The complexes undergo two reversible and well-separated one-electron reduction and oxidation processes, respectively. EPR Spectroscopy of the paramagnetic intermediates with comproportionation constants K-c > 10(12) and UV-vis-NIR spectroelectrochemistry were used to identify the accessible redox states as [(acac)(2)Ru-II(dih-R2-)Ru-II(acac)(2)](2-), [(acac)(2)Ru-II(dih-Rcenter dot-)Ru-II(acac)(2)](-), [(acac)(2)Ru-II(dih-R2-)Ru-III(acac)(2)], [(acac)(2)Ru-III(dih-Rcenter dot-)Ru-III(acac)(2)](+), and [(acac)(2)Ru-III(dih-R)Ru-III(acac)(2)](2+). Reaction of 3,6-diaryl-1,2,4,5-tetrazines (aryl = R = phenyl, 2-furyl or 2-thienyl) with 2 equiv of Ru(acac)(2)(CH3-CN)(2) results in reductive tetrazine ring opening to yield diruthenium complexes [(acac)(2)Ru-III(dih-R2-)Ru-III(acac)(2)] bridged by the new 1,2-diiminohydrazido(2-) (dih-R2- = HNC(R)NNC(R)NH2-) ligands. The complexes undergo two reversible and well-separated one-electron reduction and oxidation processes, respectively. EPR Spectroscopy of the paramagnetic intermediates with comproportionation constants K-c > 10(12) and UV-vis-NIR spectroelectrochemistry were used to identify the accessible redox states as [(acac)(2)Ru-II(dih-R2-)Ru-II(acac)(2)](2-), [(acac)(2)Ru-II(dih-Rcenter dot-)Ru-II(acac)(2)](-), [(acac)(2)Ru-II(dih-R2-)Ru-III(acac)(2)], [(acac)(2)Ru-III(dih-Rcenter dot-)Ru-III(acac)(2)](+), and [(acac)(2)Ru-III(dih-R)Ru-III(acac)(2)](2+). (en)
Title	Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system Otevření kruhu 1,2,4,5-tetrazinů indukované redukcí kovem: Tři výsledné koordinační alternativy zahrnující nový můstkový %22non-innocent%22 ligandový systém 1,2-diiminohydrazido(2-) (cs) Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system (en)
skos:prefLabel	Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system Otevření kruhu 1,2,4,5-tetrazinů indukované redukcí kovem: Tři výsledné koordinační alternativy zahrnující nový můstkový %22non-innocent%22 ligandový systém 1,2-diiminohydrazido(2-) (cs) Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system (en)
skos:notation	RIV/61388955:_____/06:00049070!RIV07-AV0-61388955
http://linked.open.../vavai/riv/strany	1316;1325
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(1P05OC068), P(IAA400400505), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	3
http://linked.open...vai/riv/dodaniDat	2007
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	433027
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/06:00049070
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	spectroscopic properties; Ru complexes; crystal-structures; redox (en)
http://linked.open.../riv/klicoveSlovo	Ru complexes crystal-structures redox spectroscopic properties
http://linked.open...odStatuVydavatele	US - Spojené státy americké
http://linked.open...ontrolniKodProRIV	[311E4DE82A57]
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	8 (xsd:int)
http://linked.open...vavai/riv/projekt	Control of functional behaviour of transition - metal compounds Redox reactions of free radicals, reactivity in presence of host molecules
http://linked.open...UplatneniVysledku	2006
http://linked.open...v/svazekPeriodika	45
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Kaim, W. Lahiri, G. K. Mobin, S. M. Sarkar, B. Maji, S. Puranik, V. G. Patra, 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	10 (xsd:int)
is http://linked.open...avai/riv/vysledek of	Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system Metal-induced reductive ring opening of 1,2,4,5-tetrazines: Three resulting coordination alternatives, including the new non-innocent 1,2-diiminohydrazido(2-) bridging ligand system

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