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**.