Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

9-2010

Journal or Book Title

Journal of Physical Chemistry A

Volume

114

Issue

38

First Page

10458

Last Page

10466

DOI

10.1021/jp1064165

Abstract

Free energies for the homolysis of the NO−C and N−OC bonds were compared for a large number of alkoxyamines at 298 and 393 K, both in the gas phase and in toluene solution. On this basis, the scope of the N−OC homolysis side reaction in nitroxide-mediated polymerization was determined. It was found that the free energies of NO−C and N−OC homolysis are not correlated, with NO−C homolysis being more dependent upon the properties of the alkyl fragment and N−OC homolysis being more dependent upon the structure of the aminyl fragment. Acyclic alkoxyamines and those bearing the indoline functionality have lower free energies of N−OC homolysis than other cyclic alkoxyamines, with the five-membered pyrrolidine and isoindoline derivatives showing lower free energies than the six-membered piperidine derivatives. For most nitroxides, N−OC homolysis is normally favored above NO−C homolysis only when a heteroatom that is α to the NOC carbon center stabilizes the NO−C bond and/or the released alkyl radical is not sufficiently stabilized. As part of this work, accurate methods for the calculation of free energies for the homolysis of alkoxyamines were determined. Accurate thermodynamic parameters to within 4.5 kJ mol−1 of experimental values were found using an ONIOM approximation to G3(MP2)-RAD combined with PCM solvation energies at the B3-LYP/6-31G(d) level.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 114 (2010): 10458, doi:10.1021/jp1064165. Copyright 2010 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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