Dimethylcuprate Undergoes a Dyotropic Rearrangement
Nicole J Rijs, Brian F Yates, Richard AJ O'Hair
CHEMISTRY-A EUROPEAN JOURNAL | WILEY-V C H VERLAG GMBH | Published : 2010
All change! Comparison of the gasphase decomposition reactions of [CH 3CuCH3]- and [CH3AgCH 3]- reveals that [CH3CuCH3] - undergoes a competition between a dyotropic rearrangement and bond homolysis, whilst [CH3AgCH3]- only undergoes bond homolysis. Ab initio calculations reveal that the different behavior in [CH3AgCH3]- stems from both the lowering of the homolytic bond dissociation energy and an increase in dyotropic rearrangement activation energy. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.
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Awarded by ARC
We thank the ARC for financial support grant DP0558430 (to R.A.J.O.). The Victorian Partnership for Advanced Computing is acknowledged for provision of computer time. N.J.R. thanks the Faculty of Science for a Science Faculty Scholarship. We thank the reviewers for valuable comments.