Table of Contents
Journal of Inorganic Chemistry
Volume 2013 (2013), Article ID 149425, 6 pages
http://dx.doi.org/10.1155/2013/149425
Research Article

Computational Study on the Intramolecular Carbene-CO Coupling in M(CH2)(CO)3 Radicals (M = Co, Rh, Ir)

MTA-TKI Research Group for Selective Chemical Syntheses, Department of Inorganic Chemistry, János Szentágothai Research Center, University of Pécs, Ifjúság Útja 6, Pécs 7624, Hungary

Received 30 September 2013; Revised 3 December 2013; Accepted 4 December 2013

Academic Editor: Arturo Espinosa

Copyright © 2013 Gábor Tollár and Tamás Kégl. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The intramolecular carbene-carbonyl coupling has been investigated for the simple M(CH2)(CO)3 (M = Co, Rh, Ir) radical complexes at the DFT PBEPBE/TZVP level of theory. The coupling is predicted to be very fast for the cobalt-containing system, but it is still feasible for the systems based on the other two metals. The back-way reaction, that is, the conversion of the ketene complex into carbonyl-carbene complex, cannot be excluded from the Ir-containing system in CH2Cl2, and it is even favored in gas phase. The intermolecular ketene formation by the addition of external CO onto the CH2 moiety is the favored pathway for the Ir-complex. The Laplacian distribution, as well as the natural spin density distribution of all the species, being involved in the reaction, gives explanation for the significant difference between the nature of the Co-complex and the Rh- and Ir-systems.