000118184 001__ 118184
000118184 005__ 20240319081018.0
000118184 0247_ $$2doi$$a10.1021/acs.organomet.2c00125
000118184 0248_ $$2sideral$$a129571
000118184 037__ $$aART-2022-129571
000118184 041__ $$aeng
000118184 100__ $$0(orcid)0000-0001-7341-0033$$aGonzález-Lainez, Miguel
000118184 245__ $$aN-Methylation of Amines with Methanol Catalyzed by Iridium(I) Complexes Bearing an N, O-Functionalized NHC Ligand
000118184 260__ $$c2022
000118184 5060_ $$aAccess copy available to the general public$$fUnrestricted
000118184 5203_ $$aA set of neutral IrBr(L-2)-(kappa C-(t)BuImCH(2)PyCH(2)OMe)] and cationic Ir(L-2)-(kappa C, N-tBuImCH(2)PyCH(2)OMe)]PF6 (L-2 = cod, (CO)(2)) Ir(I) compounds featuring a flexible lutidine-derived polydentate ligand having NHC and - OMe as donor functions have been evaluated as catalyst precursors for the N-methylation of aniline using methanol both as a reducing agent and a C1 source. The carbonyl complexes are somewhat more active than the related diene compounds with the neutral compound IrBr(CO)(2)(kappa C-(t)BuImCH(2)PyCH(2)OMe)] being the more active. A range of aromatic primary amines, including heterocyclic amines, have been selectively transformed into the corresponding N-methylamino derivatives using this catalyst at a low catalyst loading (0.1 mol %) and substoichiometric amounts of Cs2CO3 (half equiv) as a base, in methanol at 423 K. For aliphatic primary amines, selective N, N-dimethylation was achieved under the same catalytic conditions. The unselective deprotonation of the methylene linkers in IrBr(CO)(2)(kappa C-(t)BuImCH(2)PyCH(2)OMe)] affords two isomeric neutral complexes featuring a coordinated dearomatized pyridine core, which were converted into Ir(OMe)(CO)(2)(kappa C-(t)BuImCH(2)PyCH(2)OMe)] upon addition of methanol. This compound undergoes thermal activation of a C-H bond of the tert-butyl group to give the cyclometalated iridium(I) complex Ir(CO)(2){kappa C-2, C-(-CH2Me2C-ImCH(2)PyCH(2)OMe)}] featuring a bidentate C, C-coordinated NHC ligand. Mechanistic investigations support a borrowing hydrogen mechanism proceeding through iridium(I) intermediates with the methoxo complex as the catalytic active species and the cyclometalated complex as the catalyst resting state. Deuterium labeling experiments have demonstrated that both species are in equilibrium under catalytic conditions, which is consistent with the exhibited catalytic activity of the cyclometalated complex.
000118184 536__ $$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00$$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
000118184 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000118184 590__ $$a2.8$$b2022
000118184 592__ $$a0.868$$b2022
000118184 591__ $$aCHEMISTRY, ORGANIC$$b16 / 52 = 0.308$$c2022$$dQ2$$eT1
000118184 593__ $$aInorganic Chemistry$$c2022$$dQ1
000118184 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b16 / 42 = 0.381$$c2022$$dQ2$$eT2
000118184 593__ $$aPhysical and Theoretical Chemistry$$c2022$$dQ1
000118184 593__ $$aOrganic Chemistry$$c2022$$dQ1
000118184 594__ $$a6.6$$b2022
000118184 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000118184 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M. Victoria
000118184 700__ $$0(orcid)0000-0001-7904-2729$$aAzpiroz, Ramón
000118184 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000118184 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F. Javier$$uUniversidad de Zaragoza
000118184 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000118184 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000118184 773__ $$g41, 11 (2022), 1364–1380$$pOrganometallics$$tOrganometallics$$x0276-7333
000118184 8564_ $$s2897728$$uhttps://zaguan.unizar.es/record/118184/files/texto_completo.pdf$$yVersión publicada
000118184 8564_ $$s3009082$$uhttps://zaguan.unizar.es/record/118184/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000118184 909CO $$ooai:zaguan.unizar.es:118184$$particulos$$pdriver
000118184 951__ $$a2024-03-18-15:56:35
000118184 980__ $$aARTICLE