Mechanism of isomerization and methyl migration in heterobimetallic Rhenium-Iridium complexes: experimental and DFT study

Pichaandi, Kothanda Rama, Kabalan, Lara, Kais, Sabre and Abu-Omar, Mahdi M. 2016. Mechanism of isomerization and methyl migration in heterobimetallic Rhenium-Iridium complexes: experimental and DFT study. Organometallics 35 (4) , 605–611. 10.1021/acs.organomet.6b00010

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	American Chemical Society
ISSN:	0276-7333
Last Modified:	04 Mar 2021 12:00
URI:	https://orca.cardiff.ac.uk/id/eprint/139189

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