期刊
DALTON TRANSACTIONS
卷 -, 期 44, 页码 6242-6249出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/b812405a
关键词
-
资金
- Swiss National Science Foundation
Palladation of C2-protected diimidazolium salts with Pd(OAc)(2) afforded complexes comprising C4-bound N-heterocyclic dicarbene ligands. The reactivity of these complexes towards Lewis acids (AgBF4, AgOAc) and Bronsted acids (H2SO4, H3PO4, HOAc) revealed that abnormal C4 bonding of the carbenes markedly increases the nucleophilicity of the coordinated palladium center as compared to C2 bonding. Despite its formal +2 charge, the palladium center in these complexes is best described as a Lewis base. The abnormal carbene bonding mode induces new reaction patterns such as the formation of a Pd-Ag adduct. Based on metallation studies including the palladation of a dissymmetric diimidazolium salt, a rationale for the selective activation of the C4-H bond in the diimidazolium precursor salts is proposed.
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