Issue 9, 2011

Ring-opening radical clock reactions: many density functionals have difficulty keeping time

Abstract

The ability of several density-functional theory methods to describe the kinetics and energetics of a series of ring-opening reactions of cyclopropyl and cyclobutyl-type radicals was explored. PBE, B971 and B3LYP perform quite well in their ability to replicate experiment, based upon the ring opening of cyclopropylcarbinyl, two α-trialkylsilyloxycyclopropylmethyl radicals, pentamethylcyclopropylcarbinyl, cyclobutylcarbinyl and 1-cyclobutylethylcarbinyl. The other functionals tested, which includes BLYP, CAM-B3LYP, BHandHLYP, B2PLYP and B2PLYP-D, as well as functionals designed for kinetics applications, namely MPW1K, BMK and M06-2X, all perform poorly. The latter of these functionals display some integration grid dependencies.

Graphical abstract: Ring-opening radical clock reactions: many density functionals have difficulty keeping time

Supplementary files

Article information

Article type
Paper
Submitted
24 Dec 2010
Accepted
23 Feb 2011
First published
24 Feb 2011

Org. Biomol. Chem., 2011,9, 3158-3164

Ring-opening radical clock reactions: many density functionals have difficulty keeping time

I. D. Mackie and G. A. DiLabio, Org. Biomol. Chem., 2011, 9, 3158 DOI: 10.1039/C0OB01246G

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