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双卡宾钯(II)配合物。饱和与不饱和 N-杂环卡宾的反应性。

Biscarbene palladium(II) complexes. reactivity of saturated versus unsaturated N-heterocyclic carbenes.

机构信息

Department of Chemistry, National Taiwan University, Taipei 106, Taiwan.

出版信息

Inorg Chem. 2010 Mar 15;49(6):3011-8. doi: 10.1021/ic9025188.

DOI:10.1021/ic9025188
PMID:20143789
Abstract

A series of designed palladium biscarbene complexes including saturated and unsaturated N-heterocyclic carbene (NHC) moieties have been prepared by the carbene transfer methods. All of these complexes have been characterized by (1)H and (13)C NMR spectroscopy as well as X-ray diffraction analysis. The reactivity of Pd-C((saturated NHC)) is distinct from that of Pd-C((unsaturated NHC)). The Pd-C((saturated NHC)) bonds are fairly stable toward reagents such as CF(3)COOH, AgBF(4) and I(2), whereas Pd-C((unsaturated NHC)) bonds are readily cleaved under the similar conditions. Notably, the catalytically activity of these palladium complexes on Suzuki-Miyaura coupling follows the order: (sat-NHC)(2)PdCl(2) > (sat-NHC)(unsat-NHC)PdCl(2 )> (unsat-NHC)(2)PdCl(2).

摘要

一系列设计的钯双卡宾配合物,包括饱和和不饱和的 N-杂环卡宾(NHC)部分,已经通过卡宾转移方法制备。所有这些配合物都通过(1)H 和(13)C NMR 光谱以及 X 射线衍射分析进行了表征。Pd-C((饱和 NHC))的反应性与 Pd-C((不饱和 NHC))的反应性明显不同。Pd-C((饱和 NHC))键对 CF(3)COOH、AgBF(4)和 I(2)等试剂相当稳定,而 Pd-C((不饱和 NHC))键在类似条件下容易断裂。值得注意的是,这些钯配合物在 Suzuki-Miyaura 偶联反应中的催化活性遵循以下顺序:(sat-NHC)(2)PdCl(2)>(sat-NHC)(unsat-NHC)PdCl(2)>(unsat-NHC)(2)PdCl(2)。

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