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

Collins, L.R., Riddlestone, Ian M., Mahon, M.F. and Whittlesey, M.K. (2015) A Comparison of the Stability and Reactivity of Diamido- and Diaminocarbene Copper Alkoxide and Hydride Complexes Chemistry - A European Journal, 21 (40). pp. 14075-14084.

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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.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Collins, L.R.
Riddlestone, Ian M.i.riddlestone@surrey.ac.uk
Mahon, M.F.
Whittlesey, M.K.
Date : 16 September 2015
DOI : 10.1002/chem.201502476
Uncontrolled Keywords : alkoxide ligands, carbenes, copper, diamidocarbenes, hydrides
Additional Information : No further action
Depositing User : Clive Harris
Date Deposited : 19 Jun 2019 14:55
Last Modified : 19 Jun 2019 14:55
URI: http://epubs.surrey.ac.uk/id/eprint/852018

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