The complex [Ir(H)(CFSO)(NSiN)(coe)] (NSiN=bis(pyridine-2-yloxy)methylsilyl fac-coordinated) (1) is an effective catalyst precursor for the solvent-free synthesis of silyl carbamates from reaction of aliphatic secondary amines with CO and HSiMe(OSiMe). The preferential formation of the silyl carbamate instead of the expected formamide or methylamine has proven to be consequence of an iridium-catalyzed dehydrogenative Si-N coupling between the silane and the amine to afford the corresponding silyl amine, which under the reaction conditions reacts with CO to give the corresponding silyl carbamate.

The authors express their appreciation to the support from the MINECO/FEDER project CTQ2012–35665, Gobierno de Aragón (Spain) DGA/FSE-E07 and the Ministry of Higher Education, Saudi Arabia, in establishment of the Center of Research Excellence in Petroleum Refining & Petrochemicals at King Fahd University of Petroleum & Minerals (KFUPM) and the support from KFUPM-University of Zaragoza research agreement.

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