Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives

This contribution shows how a small change of a remote substituent (COOCH 3 for e.g. OCH 3) on Fischer aminocarbene complexes can change totally the LUMO location, and thus electron distribution, extent of π-electron delocalization and, consequently, redox properties of these potential catalysts. Du...

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Vydáno v:	Electrochimica acta Ročník 56; číslo 19; s. 6853 - 6859
Hlavní autoři:	Hoskovcová, Irena, Zvěřinová, Radka, Roháčová, Jana, Dvořák, Dalimil, Tobrman, Tomáš, Záliš, Stanislav, Ludvík, Jiří
Médium:	Journal Article
Jazyk:	angličtina
Vydáno:	Kidlington Elsevier Ltd 30.07.2011 Elsevier
Témata:	Bonding Carbonyl and nitrosyl metals Chemistry Chromium Derivatives DFT calculations Electrochemistry Electrode potentials Electronics Exact sciences and technology Fischer aminocarbene complexes Fittings General and physical chemistry Inorganic chemistry and origins of life Iron Kinetics and mechanism of reactions LFER LUMO location Mathematical analysis Preparations and properties Electrochemistry LUMO location Fischer aminocarbene complexes LFER DFT calculations Chromium Organic compounds Chromium Carbonyl Complexes Orbital interaction Ylidene complex Chemical reduction Ester Carboxylic acid Chlorine Organic compounds Aminocarbene Electrochemical reaction Ether Frontier orbital Benzene derivatives Theoretical study Transition metal Carbonyl Complexes Iron Organic compounds Iron Carbonyl Complexes Density functional method Fluorine Organic compounds Kinetics
ISSN:	0013-4686, 1873-3859
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Popis
Shrnutí:	This contribution shows how a small change of a remote substituent (COOCH 3 for e.g. OCH 3) on Fischer aminocarbene complexes can change totally the LUMO location, and thus electron distribution, extent of π-electron delocalization and, consequently, redox properties of these potential catalysts. During investigation of redox properties of extended series of title compounds, an exceptionally positive reduction potential was observed (non fitting the LFER plot) for p-COOR substituents. This effect is caused by a strong intramolecular electronic interaction, which is specific for p-phenylene dicarbonyl compounds. In this context, the CN bond in aminocarbene moiety has a double bond character and resembles carbonyl function. The interpretation was proved by DFT calculations.
Bibliografie:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	0013-4686 1873-3859
DOI:	10.1016/j.electacta.2011.05.096