Mechanism of Isomerization and Methyl Migration in Heterobimetallic Rhenium-Iridium Complexes

Experimental and DFT Study

Kothanda Rama Pichaandi, Lara Kabalan, Sabre Kais, Mahdi M. Abu-Omar

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Investigation of the mechanism of conversion of the bimetallic complex [PNP(H)Ir-μ(CH2)-μ(O)-Re(O)2][PF6] (1) to its structural isomer [PNP(Me)(CH3CN)Ir-ReO3][PF6] (2) by detailed kinetics and DFT computational studies is reported. The reaction proceeds by intramolecular rearrangement of 1 to [PNP(Me)Ir-ReO3][PF6] (S) via a methyl-bridged [PNP(H)Ir-μ(CH3)-Re(O)3][PF6] (P) intermediate followed by CH3CN coordination. The rate-determining step is the transformation of 1 to P displaying ΔG of 21.8 kcal/mol. Experimental kinetic results include zero-order dependence on acetonitrile, positive ΔS, and deuteration of the bridging methylidene group in the reaction of 1 with CD3OD. All of these results support the proposed mechanism.

Original languageEnglish
Pages (from-to)605-611
Number of pages7
JournalOrganometallics
Volume35
Issue number4
DOIs
Publication statusPublished - 22 Feb 2016

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Rhenium
Iridium
rhenium
Isomerization
iridium
Discrete Fourier transforms
isomerization
Kinetics
kinetics
Isomers
acetonitrile
isomers

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Mechanism of Isomerization and Methyl Migration in Heterobimetallic Rhenium-Iridium Complexes : Experimental and DFT Study. / Pichaandi, Kothanda Rama; Kabalan, Lara; Kais, Sabre; Abu-Omar, Mahdi M.

In: Organometallics, Vol. 35, No. 4, 22.02.2016, p. 605-611.

Research output: Contribution to journalArticle

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AU - Kais, Sabre

AU - Abu-Omar, Mahdi M.

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