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Unexpected migratory insertion reactions of M(alkyl)2 (M = Zn, Cd) and diamidocarbenes

Collins, L.R., Hierlmeier, G., Mahon, M.F., Riddlestone, Ian M. and Whittlesey, M.K. (2015) Unexpected migratory insertion reactions of M(alkyl)2 (M = Zn, Cd) and diamidocarbenes Chemistry - A European Journal, 21 (8). pp. 3215-3218.

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The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P4. Herein, we report that metal coordinated DACs also exhibit electrophilic reactivity, undergoing attack by Zn and Cd dialkyl precursors to afford the migratory insertion products [(6‐MesDAC‐R)MR] (M=Zn, Cd; R=Et, Me; Mes=mesityl). These species were formed via the spectroscopically characterised intermediates [(6‐MesDAC)MR2], exhibiting barriers to migratory insertion which increase in the order MR2 = ZnEt2 < ZnMe2 < CdMe2. Compound [(6‐MesDAC‐Me)CdMe] showed limited stability, undergoing deposition of Cd metal, by an apparent β‐H elimination pathway. These results raise doubts about the suitability of diamidocarbenes as ligands in catalytic reactions involving metal species bearing nucleophilic ligands (M‐R, M‐H).

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
Collins, L.R.
Hierlmeier, G.
Mahon, M.F.
Riddlestone, Ian
Whittlesey, M.K.
Date : 6 February 2015
Funders : Engineering and Physical Sciences Research Council (EPSRC)
DOI : 10.1002/chem.201406406
Uncontrolled Keywords : Alkyl ligands; Cadmium; Carbenes; Migratory insertion; Zinc
Depositing User : Clive Harris
Date Deposited : 24 Jun 2019 10:10
Last Modified : 24 Jun 2019 10:54

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