Reactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study
Title | Reactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study |
Publication Type | Journal Article |
Year of Publication | 2022 |
Authors | Agrawal, NK, Dash, SR, Vanka, K, Nethaji, M, Jagirdar, BR |
Journal | Journal of Organometallic Chemistry |
Volume | 965 |
Pagination | 122317 |
Date Published | MAY |
Type of Article | Article |
ISSN | 0022-328X |
Keywords | Hydrogenation, Insertion, iridium complex, isomerization, Oxidative addition, Reductive elimination |
Abstract | Reaction of a four coordinate, 16-electron Ir complex, [Ir-(iPr)4(POCOP)(PPh3)] (4 ) (((iPr)4)(POCOP= 2,6-bis(di-isopropyl phosphinito)benzene, kappa(3)-C6H3-1,3-[OP((iPr))(2)](2)), with H-2 resulted in an oxidative addition product, cis-dihydride complex, cis-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( cis-5 ) presumably via the intermediacy of a sigma complex, [Ir(eta(2)-H-2)((iPr)4)(POCOP)(PPh3)]. The cis-dihydride complex completely isomerizes to the trans-dihydride complex trans-[Ir(H)(2) ((iPr)4)(POCOP)(PPh3)] ( trans-5 ) under ambient conditions in about 3 h. It was found that the steric and electronic features on the iridium center have significant influence on the approach of H-2 onto the metal center followed by oxidative addition and isomerization. The isomerization process was studied in detail and all the mechanistic aspects have been elucidated using a combination of both experimental work and computation. The cis-dihydride complex isomerizes to the trans-dihydride by compensating the trans influence of the strongly trans-directing hydride ligand. A mechanism involving the exchange of the position of PPh3 with a hydride ligand cis to itself via PPh3 dissociation and re-coordination thereby resulting in the formation of the trans-dihydride complex, has been proposed for the isomerization. The cis-dihydride was found to be a highly active catalyst for hydrogenation of ethy-lene. A competing reactivity study of cis-dihydride between isomerization versus insertion of C2H4 into the Ir-H bond, was studied experimentally and computationally. (c) 2022 Elsevier B.V. All rights reserved. |
DOI | 10.1016/j.jorganchem.2022.122317 |
Type of Journal (Indian or Foreign) | Foreign |
Impact Factor (IF) | 2.345 |
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