Mechanism of Hydrogenolysis of an Iridium–Methyl Bond: Evidence for a Methane Complex Intermediate
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https://figshare.com/articles/dataset/Mechanism_of_Hydrogenolysis_of_an_Iridium_Methyl_Bond_Evidence_for_a_Methane_Complex_Intermediate/2448763
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资源简介：
Evidence for key σ-complex intermediates in the
hydrogenolysis
of the iridium–methyl bond of (PONOP)Ir(H)(Me)+ (1) [PONOP = 2,6-bis(di-tert-butylphosphinito)pyridine]
has been obtained. The initially formed η2-H2 complex, 2, was directly observed upon treatment
of 1 with H2, and evidence for reversible
formation of a σ-methane complex, 5, was obtained
through deuterium scrambling from η2-D2 in 2-d2 into the methyl group of 2 prior to methane loss.
This sequence of reactions was modeled by density functional theory
calculations. The transition state for formation of 5 from 2 showed significant shortening of the Ir–H
bond for the hydrogen being transferred; no true Ir(V) trihydride
intermediate could be located. Barriers to methane loss from 2 were compared to those of 1 and the six-coordinate
species (PONOP)Ir(H)(Me)(CO)+ and (PONOP)Ir(H)(Me)(Cl).
创建时间：
2013-01-30
