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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F10%3A00342383" target="_blank" >RIV/61388955:_____/10:00342383 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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 andpropylene 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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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 andpropylene 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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CG - Elektrochemie

OECD FORD obor

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Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2010

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Organometallic Chemistry

ISSN

0022-328X

e-ISSN

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Svazek periodika

695

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

7

Strana od-do

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Kód UT WoS článku

000275619800024

EID výsledku v databázi Scopus

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