RT Journal Article
T1 Mechanism of Side Reactions in Alkane C-H Bond Functionalization by Diazo Compounds Catalyzed by Ag and Cu Homoscorpionate Complexes—A DFT Study
A1 Braga, Ataualpa A. C.
A1 Caballero Bevia, Ana
A1 Urbano Baena, Juan
A1 Díaz Requejo, María Mar
A1 Pérez Romero, Pedro José
A1 Maseras, Feliu
AB DFT computational methods were applied to the mechanistic study of the formation of fumarate and maleate derivatives in a solution containing alkane, TpBr3M [M=Cu, Ag; TpBr3=hydrotris(3,4,5-tribromopyrazolyl)borate] and methyl diazoacetate. These solutions are the experimentally reported conditions for carbene insertion into alkane C-H bonds, a procedure that usually competes with a nondesired reaction, producing fumarate and/or maleate derivatives. Several mechanisms are analyzed. The preferred mechanism proceeds through a direct reaction between a metallocarbene complex intermediate and a diazo molecule. The computational results explain all of the available experimental evidence and provide important information on the behavior of these systems.
PB Wiley-VCH Verlag
SN 1867-3880
SN 1867-3899 (electrónico)
YR 2011
FD 2011
LK http://hdl.handle.net/10272/11564
UL http://hdl.handle.net/10272/11564
LA eng
NO Braga, A.A.C., Caballero Bevia, A., Urbano Baena, J., Díaz Requejo, M.M., Pérez Romero, P.J., Maseras, F.: "Mechanism of Side Reactions in Alkane C-H Bond Functionalization by Diazo Compounds Catalyzed by Ag and Cu Homoscorpionate Complexes—A DFT Study". ChemCatChem. Vol. 3, n. 10, págs. 1646–1652, (2011). DOI: 10.1002/cctc.201100082
NO Financial support from the ICIQ foundation, the Spanish MICINN (CTQ2008-06866-CO2-02/BQU, CTQ2008-00042/BQU), Consolider Ingenio 2010 (CSD2006-0003,) and the Catalan DIUE (2009SGR0259) is acknowledged.
DS Repositorio Institucional de la Universidad de Huelva
RD 1 jun 2026