Ab Initio Study of the
SN1Ar and SN2Ar Reactions of Benzenediazonium Ion
with Water. On the Conception of "Unimolecular Dediazoniation" in
Solvolysis Reactions
Zhengyu
Wu and Rainer Glaser*
Department of Chemistry
University
of Missouri-Columbia
Columbia, Missouri, 65211 (USA)
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Figure 1. Molecular models of the stationary
minima structures relevant to the benzenediazonium ion hydrolysis
reaction.
The
structures of benzenediazonium ion (RHF, MP2(full), B3LYP),
protonated phenol (RHF, MP2(full), B3LYP),
phenyl cation (RHF, MP2(full) B3LYP),
pre-coordination complex (RHF, MP2(full), B3LYP),
and post-coordination complex (RHF, MP2(full), B3LYP).
Figure 2.
Transition state structures involved in the hydrolysis of benzenediazonium
ion.
The structures of transition state of the bimolecular pathway TS1a and TS1b determined at RHF/6-31G**,
TS2a and TS2b (transition
vector animation) determined at MP2(full)/6-31G**, and
TS3a, TS1b and TS3c
determined at B3LYP/6-31G**.