A Comparison of the Stability and Reactivity of Diamido- and Diaminocarbene Copper Alkoxide and Hydride Complexes

The mononuclear N-heterocyclic carbene (NHC) copper alkoxide complexes [(6-NHC)CuOtBu] (6-NHC=6-MesDAC (1), 6-Mes (2)) have been prepared by addition of the free carbenes to the tetrameric tert-butoxide precursor [Cu(OtBu)](4), or by protonolysis of [(6-NHC)CuMes] (6-NHC=6-MesDAC (3), 6-Mes (4)) with tBuOH. In contrast to the relatively stable diaminocarbene complex 2, the diamidocarbene derivative 1 proved susceptible to both thermal and hydrolytic ring-opening reactions, the latter affording [(6-MesDAC)Cu(OC(O)CMe2C(O)N(H)Mes)(CNMes)] (6). The intermediacy of [(6-MesDAC) Cu(OH)] in this reaction was supported by the generation of Cu2O as an additional product. Attempts to generate an isolable copper hydride complex of the type [(6-MesDAC)CuH] by reaction of 1 with Et3SiH resulted instead in migratory insertion to generate [(6-MesDAC-H)Cu(P(p-tolyl)(3))] (9) upon trapping by P(p-tolyl)(3). Migratory insertion was also observed during attempts to prepare [(6-Mes)CuH], with [(6-Mes-H)Cu(6-Mes)] (10) isolated, following a reaction that was significantly slower than in the 6-MesDAC case. The longer lifetime of [(6-Mes)CuH] allowed it to be trapped stoichiometrically by alkyne, and also employed in the catalytic semi-reduction of alkynes and hydrosilylation of ketones.