期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 8, 页码 3215-3218出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201406406
关键词
alkyl ligands; cadmium; carbenes; migratory insertion; zinc
资金
- University of Bath
- EPSRC
- EPSRC [EP/J009962/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/J009962/1] Funding Source: researchfish
The electrophilic character of free diamidocarbenes (DACs) allows them to activate inert bonds in small molecules, such as NH3 and P-4. 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).
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