title: Unexpected migratory insertion reactions of M(alkyl)2 (M=Zn, Cd) and diamidocarbenes.
abstract: 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).
authors.affiliation: Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY (UK), Fax: (+44) 1225-386-231.
authors.forename: Lee R
authors.initials: LR
authors.lastname: Collins
authors.forename: Gabriele
authors.initials: G
authors.lastname: Hierlmeier
authors.forename: Mary F
authors.initials: MF
authors.lastname: Mahon
authors.forename: Ian M
authors.initials: IM
authors.lastname: Riddlestone
authors.forename: Michael K
authors.initials: MK
authors.lastname: Whittlesey
keywords: alkyl ligands; cadmium; carbenes; migratory insertion; zinc