000148787 001__ 148787
000148787 005__ 20250121150754.0
000148787 0247_ $$2doi$$a10.1021/acs.inorgchem.4c04512
000148787 0248_ $$2sideral$$a142026
000148787 037__ $$aART-2025-142026
000148787 041__ $$aeng
000148787 100__ $$aPadilla, Marina
000148787 245__ $$aCross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species
000148787 260__ $$c2025
000148787 5060_ $$aAccess copy available to the general public$$fUnrestricted
000148787 5203_ $$aAn active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range of secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L = coe, X = Cl, 2; L = coe, X = OTf, 3; L = PCy3, X = Cl, 4; L = PCy3, X = OTf, 5), which are stabilized by a weak yet noticeable Ir···H–C agostic interaction between the iridium and one of the C–H bonds of the 8-Me substituent of the NSiDMQ ligand, have been prepared and fully characterized. These species have proven to be effective catalysts for the CDC of secondary amines with hydrosilanes. The best catalytic performance (TOF1/2 = 79,300 h–1) was obtained using 5 (0.25 mol %), N-methylaniline, and HSiMe2Ph. The catalytic activity of the species [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ = {quinoline-2-yloxy}dimethylsilyl) and [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ = {4-methylquinoline-2-yloxy}dimethylsilyl), related to 5 but lacking the 8-Me substituent, is markedly lower than that found for 5. This fact highlights the crucial role of the 8-Me substituent of the NSiDMQ ligand in enhancing the catalytic performance of these iridium complexes.
000148787 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2022-139318NB-I00$$9info:eu-repo/grantAgreement/ES/AEI/RED2022-134331-T$$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
000148787 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000148787 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000148787 700__ $$aBatuecas, María$$uUniversidad de Zaragoza
000148787 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000148787 700__ $$aFernández, Israel
000148787 700__ $$0(orcid)0000-0002-0497-1969$$aFernández-Álvarez, Francisco J.$$uUniversidad de Zaragoza
000148787 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000148787 773__ $$g64, 1 (2025), 255-267$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000148787 8564_ $$s4283685$$uhttps://zaguan.unizar.es/record/148787/files/texto_completo.pdf$$yVersión publicada
000148787 8564_ $$s2684332$$uhttps://zaguan.unizar.es/record/148787/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000148787 909CO $$ooai:zaguan.unizar.es:148787$$particulos$$pdriver
000148787 951__ $$a2025-01-21-14:45:32
000148787 980__ $$aARTICLE