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

0361581 - ÚFCH JH 2012 RIV GB eng J - Journal Article
Hoskovcová, I. - Zvěřinová, R. - Roháčová, J. - Dvořák, D. - Tobrman, T. - Záliš, Stanislav - Ludvík, Jiří
Fischer aminocarbene complexes of chromium and iron: Anomalous electrochemical reduction of p-carbonyl substituted derivatives.
Electrochimica acta. Roč. 56, č. 19 (2011), s. 6853-6859. ISSN 0013-4686. E-ISSN 1873-3859
R&D Projects: GA AV ČR IAA400400813
Institutional research plan: CEZ:AV0Z40400503
Keywords : DFT calculations * electrochemistry * Fischer aminocarbene complexes
Subject RIV: CG - Electrochemistry
Impact factor: 3.832, year: 2011

This contribution shows how a small change of a remote substituent (COOCH3 for e.g. OCH3) 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.
Permanent Link: http://hdl.handle.net/11104/0198867