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

Autor:	Irena Hoskovcová, Radka Zvěřinová, Stanislav Záliš, Tomáš Tobrman, Jiří Ludvík, Jana Roháčová, Dalimil Dvořák
Rok vydání:	2011
Předmět:	chemistry.chemical_classification Double bond General Chemical Engineering Substituent Context (language use) Photochemistry Medicinal chemistry Redox chemistry.chemical_compound Delocalized electron chemistry Intramolecular force Electrochemistry Moiety HOMO/LUMO
Zdroj:	Electrochimica Acta. 56:6853-6859
ISSN:	0013-4686
DOI:	10.1016/j.electacta.2011.05.096
Popis:	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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::522435ac6aa9da3867af0f8e6f9c3e13 https://doi.org/10.1016/j.electacta.2011.05.096 Zobrazit plný text záznamu Full Text from ScienceDirect