About: The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

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About: The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure Goto Sponge NotDistinct Permalink

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rdf:type	skos:Concept http://linked.opendata.cz/ontology/domain/vavai/Vysledek
Description	Oxidation of the unambiguously characterized iridium(III)-enediamido complex IrCp(RNCHCHNR), R = 2,6-dimethylphenyl, with six cyclically arranged p electrons was investigated using EPR and UV-vis spectroelectrochemistry. In contrast to a corresponding iminocatecholato system reported recently by Rauchfuss et al. [27] the two one-electron oxidation steps are not completely reversible, depending on the solvent. We attribute the electrochemical behavior observed in weakly coordinating dichloromethane and propylene carbonate solvents to an enhanced propensity for ligand addition: while neutral IrCp(RNCHCHNR) remains coordinatively unsaturated with the strongly sigma and pi donating enediamido(2-) ligand mitigating the electron deficit, the oxidation to the less donating radical anion ligand (RNCHCHNR)(center dot-) or even to neutral 1,4-diazabutadiene is considered to induce a strong tendency for quasi-hexacoordination in [IrCp(L)(RNCHCHNR)], L = solvent, halide, substrate. Oxidation of the unambiguously characterized iridium(III)-enediamido complex IrCp(RNCHCHNR), R = 2,6-dimethylphenyl, with six cyclically arranged p electrons was investigated using EPR and UV-vis spectroelectrochemistry. In contrast to a corresponding iminocatecholato system reported recently by Rauchfuss et al. [27] the two one-electron oxidation steps are not completely reversible, depending on the solvent. We attribute the electrochemical behavior observed in weakly coordinating dichloromethane and propylene carbonate solvents to an enhanced propensity for ligand addition: while neutral IrCp(RNCHCHNR) remains coordinatively unsaturated with the strongly sigma and pi donating enediamido(2-) ligand mitigating the electron deficit, the oxidation to the less donating radical anion ligand (RNCHCHNR)(center dot-) or even to neutral 1,4-diazabutadiene is considered to induce a strong tendency for quasi-hexacoordination in [IrCp(L)(RNCHCHNR)], L = solvent, halide, substrate. (en)
Title	The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure (en)
skos:prefLabel	The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure (en)
skos:notation	RIV/61388955:_____/10:00342383!RIV11-MSM-61388955
http://linked.open...avai/riv/aktivita	P Z
http://linked.open...avai/riv/aktivity	P(KAN100400702), P(OC 139), P(OC09043), Z(AV0Z40400503)
http://linked.open...iv/cisloPeriodika	7
http://linked.open...vai/riv/dodaniDat	2011
http://linked.open...aciTvurceVysledku	Fiedler, Jan Záliš, Stanislav
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	300819
http://linked.open...ai/riv/idVysledku	RIV/61388955:_____/10:00342383
http://linked.open...riv/jazykVysledku	eng - angličtina
http://linked.open.../riv/klicovaSlova	1,4-diazabutadiene; electronic structure; iridium compounds (en)
http://linked.open.../riv/klicoveSlovo	electronic structure 1 4-diazabutadiene iridium compounds
http://linked.open...odStatuVydavatele	CH - Švýcarská konfederace
http://linked.open...ontrolniKodProRIV	[F6FA0C9D328B]
http://linked.open...i/riv/nazevZdroje	Journal of Organometallic Chemistry
http://linked.open...in/vavai/riv/obor	CG
http://linked.open...ichTvurcuVysledku	2 (xsd:int)
http://linked.open...cetTvurcuVysledku	6 (xsd:int)
http://linked.open...vavai/riv/projekt	Nanostructured materials for catalytic, electrocatalytic and sorption applications http://linked.opendata.cz/resource/domain/vavai/projekt/OC%20139 Properties and dynamics of electronic states of transition metal complexes
http://linked.open...UplatneniVysledku	2010
http://linked.open...v/svazekPeriodika	695
http://linked.open...iv/tvurceVysledku	Fiedler, Jan Sarkar, B. Sieger, M. Záliš, Stanislav Greulich, S. Kaim, A.
http://linked.open...ain/vavai/riv/wos	000275619800024
http://linked.open...n/vavai/riv/zamer	Struktura, reaktivita a dynamika molekulárních a biomolekulárních systémů: teorie, experiment, aplikace
issn	0022-328X
number of pages	7 (xsd:int)
is http://linked.open...avai/riv/vysledek of	The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure

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