02512nas a2200265   4500008004100000022001400041245010800055210006900163260000800232300001100240490000800251520162600259653001801885653001401903653002001917653001801937653002301955653002601978100002302004700002102027700001702048700002602065700002502091856013002116       2022                        eng d  a0022-328X00aReactivity of four coordinate iridium complex towards hydrogen: an experimental and computational study0 aReactivity of four coordinate iridium complex towards hydrogen a  cMAY  a1223170 v9653 a<p>
	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.</p>
10aHydrogenation10aInsertion10airidium complex10aisomerization10aOxidative addition10aReductive elimination1 aAgrawal, Nisha, K.1 aDash, Soumya, R.1 aVanka, Kumar1 aNethaji, Munirathinam1 aJagirdar, Balaji, R.  uhttps://library.ncl.res.in/content/reactivity-four-coordinate-iridium-complex-towards-hydrogen-experimental-and-computational