Cycloaddition reactions of metalloaromatic complexes of iridium and rhodium: A mechanistic DFT investigation

Mark A. Iron, Jan M L Martin, Milko van der Boom

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The mechanistic details of 1,2- and 1,4-cycloaddition reactions of acetone, CO2, and CS2 to isostructural iridiabenzene, iridiapyrylium, and iridiathiabenzene complexes, as well as their rhodium analogues, were elucidated by density functional theory (DFT) at the PCM/mPW1K/SDB-cc-pVDZ//mPW1K/ SDD level of theory. The calculated reaction profiles concur with reported experimental observations. It was found that the first complex reacts via a concerted reaction mechanism, while the latter two react by a stepwise mechanism. Several factors affecting the reaction mechanisms and outcome were identified. They include the composition and size of the metal-aromatic ring, the length of the substrate C=X (X = O, S) bond, the geometry of the product, the symmetry of the frontier molecular orbitals, and the type of reaction mechanism involved.

Original languageEnglish
Pages (from-to)11702-11709
Number of pages8
JournalJournal of the American Chemical Society
Issue number38
Publication statusPublished - Sep 24 2003


ASJC Scopus subject areas

  • Chemistry(all)

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