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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Bibliographic Details
Published in:Electrochimica acta Vol. 56; no. 19; pp. 6853 - 6859
Main Authors: Hoskovcová, Irena, Zvěřinová, Radka, Roháčová, Jana, Dvořák, Dalimil, Tobrman, Tomáš, Záliš, Stanislav, Ludvík, Jiří
Format: Journal Article
Language:English
Published: Kidlington Elsevier Ltd 30.07.2011
Elsevier
Subjects:
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
Online Access:Get full text
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Summary: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.
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ISSN:0013-4686
1873-3859
DOI:10.1016/j.electacta.2011.05.096