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Article on the mechanism of hydrogenolysis of an iridium methyl bond and evidence for a methane complex intermediate.
Physical Description
4 p.: ill.
Notes
Reprinted with permission from the Journal of the American Chemical Society. Copyright 2013 American Chemical Society.
Abstract: Evidence for key σ-complex intermediates in the hydrogenolysis of the irdium 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 the methane loss. This sequence of reactions was modeled by density functional theory calculations. The transition state for formation of 5 form 2 showed significant shortening of the Ir H bond for the hydrogen being transferred; no true Ir(V) trihydride intermediate could be located. Barrier 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).
Publication Title:
Journal of the American Chemical Society
Volume:
135
Issue:
4
Page Start:
1217
Page End:
1220
Peer Reviewed:
Yes
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Campos, Jesus; Kundu, Sabuj; Pahls, Dale R.; Brookhart, Maurice S.; Carmona, Ernesto & Cundari, Thomas R., 1964-.Mechanism of Hydrogenolysis of an Iridium Methyl Bond: Evidence for a Methane Complex Intermediate,
article,
January 11, 2013;
[Washington, D.C.].
(https://digital.library.unt.edu/ark:/67531/metadc179686/:
accessed April 19, 2024),
University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu;
crediting UNT College of Arts and Sciences.