物理化学学报 >> 1998, Vol. 14 >> Issue (08): 725-730.doi: 10.3866/PKU.WHXB19980811

研究论文 上一篇    下一篇

Pd(Hmp)2(PBn3)2的合成、晶体结构及其二聚机理

康北笙, 郑康成, 张华新, 童叶翔, 温庭斌, 曹荣   

  1. 中山大学化学与化学工程学院，广州 510275|结构化学国家重点实验室，中国科学院福建物质结构研究所，福州 350002
  • 收稿日期:1997-11-03 修回日期:1998-03-06 发布日期:1998-08-15
  • 通讯作者: 康北笙

Synthesis and Structure of Pd(Hmp)2(PBn3)2 and the Mechanism of its Dimerization

Kang Bei-Sheng, Zheng Kang-Cheng, Zhang Hua-Xin, Tong Ye-Xiang, Wen Ting-Bin, Cao Rong   

  1. School of Chemistry and Chemical Engineering,Zhongshan University,Guanghzou 510275|State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure Matter,Chinese Academy of Sciences,Fujian 350002
  • Received:1997-11-03 Revised:1998-03-06 Published:1998-08-15
  • Contact: Kang Bei-Sheng

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摘要：

膦巯混合配位钯化合物Pd(Hmp)2（PBu3n）2（1）含有四方平面构型的二价钯，Pd-S和Pd-P的键长分别为2.338（1）Å和2.336（1）Å，在过量的邻巯基苯酚存在下生成．如果是膦过量，则生成双核配合物Pd2（Hmp）2（PBu3n）2Cl2（2）[1]．文中讨论了（1）和（2）的生成机理和Pd（Hmp）2（PMe3）2的量化计算结果．

关键词: 膦混合配位钯化合物, 分子结构, 邻基苯酚, 生成机制, 量化计算

Abstract:

The mixed phosphine thiolato palladium complex Pd(Hmp)_2(PBu_3n)_2 (1) has the Pd(Ⅱ) in a square planar (environment with Pd-S and Pd-P being 2.338(1) Å and 2.336(1) Å, respectively. It was obtained from the reaction of PbCl_2 with phosphine in the presence of an excess of o-mercaptophenol. In excess of phosphine, the product obtained will be the dinuclear complexPd_2 (Hmp )_2 (PBu_3n )_2Cl_2 (2). The mechanism of formation of (1) and (2) and the quantum chemical calculations on a simplified model of (1) are also discussed.

Key words: Mixed phosphine thiolato palladium complex, Molecular strusture, o-Mercaptophenol, Tri-n-butylphosphine, Formation mechanism, Quantum chemical calculation