Abstract

Rhodium(I) silylamide complexes supported by the 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand have been prepared and their structures and reactivity studied. Although the complexes degrade over time to release the corresponding silylamines, they react cleanly with silver(I) salts to transfer the amido group at ambient temperature. The bis(trimethylsilyl)amide complex (dtbpe)Rh–N(TMS)2 reacts with CO2 to form a carbamate complex that decomposes via loss of hexamethyldisiloxane to form a bis(μ-isocyanate) dimer, suggesting that silylamides may be useful nitrene-group and nitrogen-atom sources through selective N–Si bond cleavage.

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