Metallabenzene versus Cp complex formation: a DFT investigation

Mark A Iron; Jan M L Martin; Milko E van der Boom

doi:10.1021/ja037983v

Metallabenzene versus Cp complex formation: a DFT investigation

J Am Chem Soc. 2003 Oct 29;125(43):13020-1. doi: 10.1021/ja037983v.

Authors

Mark A Iron¹, Jan M L Martin, Milko E van der Boom

Affiliation

¹ Department of Organic Chemistry, Weizmann Institute of Science, 76100 Rehovot, Israel.

PMID: 14570463
DOI: 10.1021/ja037983v

Abstract

One common reaction that metallabenzene complexes undergo is the formation of cyclopentadienyl (Cp) complexes. Density functional theory (DFT) was used here to investigate the reaction mechanism. It was found that the reaction can proceed via a carbene migratory insertion class of C-C coupling. Cp complexes are found to be thermodynamically favored, except for the case of (C5H5Ir)(PH3)2Cl2 (1j) where the metallabenzene was favored. Isolation a rhodiabenzene of the type (C5H5Rh)(PH3)2Cl2 (1m) and a palladiabenzene, such as (C5H5Pd)Cp (1p), may be possible.