Synthesis and Reactivity of Three-Coordinate (dtbpe)Rh Silylamides: CO2 Bond Cleavage by a Rhodium(I) Disilylamide

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.