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

• DOI: 10.1021/om401130q
• Publication Date: 2014-03-07T12:13:06Z
• Authors: Matthew T. Whited; Alex J. Kosanovich; Daron E. Janzen
• Keywords: Reactivity; Hexamethyldisiloxane; Nitrene; Trimethylsilyl; Amide; Isocyanate; Bond cleavage; Cleavage (geology)

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