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Mechanism of Side Reactions in Alkane CH Bond Functionalization by Diazo Compounds Catalyzed by Ag and Cu Homoscorpionate Complexes—A DFT Study
Author(s) -
Braga Ataualpa A. C.,
Caballero Ana,
Urbano Juan,
DiazRequejo M. Mar,
Pérez Pedro J.,
Maseras Feliu
Publication year - 2011
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201100082
Subject(s) - diazo , alkane , chemistry , carbene , surface modification , molecule , reaction mechanism , boron , catalysis , ethyl diazoacetate , combinatorial chemistry , photochemistry , medicinal chemistry , organic chemistry , cyclopropanation
DFT computational methods were applied to the mechanistic study of the formation of fumarate and maleate derivatives in a solution containing alkane, Tp Br3 M [M=Cu, Ag; Tp Br3 =hydrotris(3,4,5‐tribromopyrazolyl)borate] and methyl diazoacetate. These solutions are the experimentally reported conditions for carbene insertion into alkane CH 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.