Projects per year
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 beta-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).
|Number of pages||4|
|Journal||Chemistry - A European Journal|
|Early online date||8 Jan 2015|
|Publication status||Published - Feb 2015|
FingerprintDive into the research topics of 'Unexpected Migratory Insertion Reactions of M(alkyl)2 (M = Zn, Cd) and Diamidocarbenes'. Together they form a unique fingerprint.
- 1 Finished
Catalytic Functionalisation of Aromatic Fluorocarbons
Engineering and Physical Sciences Research Council
24/07/12 → 22/01/16
Project: Research council
- Department of Chemistry - Deputy Head of Department
Person: Research & Teaching
MC2- Nuclear Magnetic Resonance (NMR)Material and Chemical Characterisation (MC2)
Facility/equipment: Technology type