doi:10.1039/c8dt05070hengGuzmán, JeffersonBernal, Ana M.García-Orduña, PilarLahoz, Fernando J.Oro, Luis A.Fernández-Alvarez, Francisco J.Selective reduction of formamides to O-silylated hemiaminals or methylamines with HSiMe2Ph catalyzed by iridium complexesART-2019-111523The reaction of (4-methyl-pyridin-2-iloxy)ditertbutylsilane (NSi tBu -H, 1) with [IrCl(coe) 2 ] 2 affords the iridium(iii) complex [Ir(H)(Cl)(¿ 2 -NSi tBu )(coe)] (2), which has been fully characterized including X-ray diffraction studies. The reaction of 2 with AgCF 3 SO 3 leads to the formation of species [Ir(H)(CF 3 SO 3 )(¿ 2 -NSi tBu )(coe)] (3). The iridium complexes 2 and 3 are effective catalysts for the reduction of formamides with HSiMe 2 Ph. The selectivity of the reduction process depends on the catalyst. Thus, by using complex 2, with a chloride ancillary ligand, it has been possible to selectively obtain the corresponding O-silylated hemiaminal by reaction of formamides with one equivalent of HSiMe 2 Ph, while complex 3, with a triflate ligand instead of chloride, catalyzed the selective reduction of formamides to the corresponding methylamine.2019http://zaguan.unizar.es/record/13030710.1039/c8dt05070hhttp://zaguan.unizar.es/record/130307oai:zaguan.unizar.es:130307info:eu-repo/grantAgreement/ES/DGA-FSE/E07info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-PDalton Transactions 48, 13 (2019), 4255-4262All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess