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

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4 Citations (Scopus)


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
Issue number4
Publication statusPublished - 22 Feb 2016


ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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