Strong Bond Cleavage Promoted By Silyl Group
Migration In A Coordination Sphere
Author(s)
H. Nakazawa
Abstract
C-CN bond cleavage in organonitriles was attained in the photoreaction with
HSiEt3 in the presence of a catalytic amount of (5-C5H5)Fe(CO)2Me. The
reaction sequence was proposed, where silyl migration from Fe to N in the
coordinating nitrile is a key step. DFT calculations proposed a silyl migration
with small activation energy of 4.0 kcal/mol and subsequent C-CN bond
cleavage on the Fe coordination sphere. N-CN bond cleavage in cyanamide
(R2NCN) was also attained by a transition metal catalyst. A catalytic cycle was
proposed where a silyl migration from a transition metal to the nitrile nitrogen is
involved. An N-silylated 2-amidino complex was isolated, which was shown to
be an intermediate in the catalytic pathway.
Keywords: C-C bond cleavage, C-N bond cleavage, transition metal catalysis,
silyl migration.
1 Introduction
Investigations of selective bond cleavage as well as selective bond formation of
chemical compounds is important from the viewpoint of atom efficiency, low
environmental load, and sustainable chemistry. Weak bond cleavage is not so
difficult, whereas strong bond cleavage with keeping weak bonds intact is quite
difficult. Therefore, selective strong bond cleavage is a challenging topic in
chemistry. One of the promising ways to overcome the difficulties is using a
transition metal catalyst.
As the carbon-carbon bond is relatively unreactive, C-C bond cleavage is an
area of considerable current interest [1]. In particular, C-C bond activation in
Keywords
C-C bond cleavage, C-N bond cleavage, transition metal catalysis,
silyl migration
Related Book
Other papers in this volume
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