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- Title
Unexpected Migratory Insertion Reactions of M(alkyl)<sub>2</sub> (M=Zn, Cd) and Diamidocarbenes.
- Authors
Collins, Lee R.; Hierlmeier, Gabriele; Mahon, Mary F.; Riddlestone, Ian M.; Whittlesey, Michael K.
- 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).
- Subjects
ELECTROPHILES; MIGRATION reactions (Chemistry); CHEMICAL reactions; ORGANOMETALLIC chemistry; INSERTION reactions (Chemistry)
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 8, p3215
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201406406