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

SYSNO ASEP	0342383
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	The 1,4-diazabutadiene/1,2-enediamido non-innocent ligand system in the formation of iridaheteroaromatic compounds: Spectroelectrochemistry and electronic structure
Author(s)	Kaim, A. (DE) Sieger, M. (DE) Greulich, S. (DE) Sarkar, B. (DE) Fiedler, Jan (UFCH-W)_{RID, ORCID} Záliš, Stanislav (UFCH-W)_{RID, ORCID}
Source Title	Journal of Organometallic Chemistry. - : Elsevier - ISSN 0022-328X Roč. 695, č. 7 (2010), s. 1052-1058
Number of pages	7 s.
Language	eng - English
Country	CH - Switzerland
Keywords	1,4-diazabutadiene ; electronic structure ; iridium compounds
Subject RIV	CG - Electrochemistry
R&D Projects	KAN100400702 GA AV ČR - Academy of Sciences of the Czech Republic (AV ČR)
	OC 139 GA MŠMT - Ministry of Education, Youth and Sports (MEYS)
	OC09043 GA MŠMT - Ministry of Education, Youth and Sports (MEYS)
CEZ	AV0Z40400503 - UFCH-W (2005-2011)
UT WOS	000275619800024
DOI	10.1016/j.jorganchem.2009.11.042
Annotation	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.
Workplace	J. Heyrovsky Institute of Physical Chemistry
Contact	Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196
Year of Publishing	2011

Number of the records: 1