title: A Comparison of the Stability and Reactivity of Diamido- and Diaminocarbene Copper Alkoxide and Hydride Complexes.
abstract: 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.
authors: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (UK), Fax: (+44) 1225-386-231.
authors: Lee R
authors: LR
authors: Collins
authors: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (UK), Fax: (+44) 1225-386-231.
authors: Ian M
authors: IM
authors: Riddlestone
authors: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (UK), Fax: (+44) 1225-386-231. m.f.mahon@bath.ac.uk.
authors: Mary F
authors: MF
authors: Mahon
authors: Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY (UK), Fax: (+44) 1225-386-231. m.k.whittlesey@bath.ac.uk.
authors: Michael K
authors: MK
authors: Whittlesey
keywords: alkoxide ligands; carbenes; copper; diamidocarbenes; hydrides