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- W2337569353 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." @default.
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- W2337569353 date "2016-02-03" @default.
- W2337569353 modified "2023-09-26" @default.
- W2337569353 title "Mechanism of Isomerization and Methyl Migration in Heterobimetallic Rhenium–Iridium Complexes: Experimental and DFT Study" @default.
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- W2337569353 doi "https://doi.org/10.1021/acs.organomet.6b00010" @default.
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