Mechanism of Isomerization and Methyl Migration in Heterobimetallic Rhenium–Iridium Complexes: Experimental and DFT Study
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https://figshare.com/articles/dataset/Mechanism_of_Isomerization_and_Methyl_Migration_in_Heterobimetallic_Rhenium_Iridium_Complexes_Experimental_and_DFT_Study/2078167
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资源简介：
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.
创建时间：
2016-08-05
