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

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

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

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
Volume125
Issue number38
DOIs
Publication statusPublished - Sep 24 2003

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Iridium
Rhodium
Cycloaddition
Pulse code modulation
Cycloaddition Reaction
Molecular orbitals
Acetone
Density functional theory
Metals
Geometry
Substrates
Chemical analysis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Cycloaddition reactions of metalloaromatic complexes of iridium and rhodium : A mechanistic DFT investigation. / Iron, Mark A.; Martin, Jan M L; van der Boom, Milko.

In: Journal of the American Chemical Society, Vol. 125, No. 38, 24.09.2003, p. 11702-11709.

Research output: Contribution to journalArticle

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