Chin. J. Org. Chem. ›› 2019, Vol. 39 ›› Issue (8): 2183-2187.DOI: 10.6023/cjoc201905001 Previous Articles     Next Articles

Special Issue: 陈茹玉先生诞辰100周年



陈铁桥a, 刘龙a, 黄添增a, 韩立彪b   

  1. a 海南大学化学工程与技术学院 热带岛屿资源先进材料教育部重点实验室 海口 570228;
    b 日本产业技术综合研究所 筑波 305-8565 日本
  • 收稿日期:2019-05-01 修回日期:2019-06-19 发布日期:2019-07-09
  • 通讯作者: 韩立彪
  • 基金资助:


Synthesis and Reactivity of Group 10 Transition Metal Complexes with Alkenylphosphoryl Compounds

Chen Tieqiaoa, Liu Longa, Huang Tianzenga, Han Li-Biaob   

  1. a Key Laboratory of Ministry of Education for Advanced Materials in Tropical Island Resources, College of Chemical Engineering and Technology, Hainan University, Haikou, Hainan 570228, China;
    b National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
  • Received:2019-05-01 Revised:2019-06-19 Published:2019-07-09
  • Contact: 10.6023/cjoc201905001
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21871070), and the Natural Science Foundation of Hainan Province (No. 219MS005).

Alkenylphosphoryl compounds could quickly replace two phosphine ligands in Pd(PEt3)4 at room temperature to produce the corresponding palladium complexes 3a~3e in high yields. Similar nickel and platinium complexes 3f and 3g were also synthesized by the reaction. Complex 3e could react with HOAc to release alkenylphosphoryl compounds gradually. By further addition of 2 equiv. of PEt3, the reaction could take place completely, generating a phosphoniun 4 as a precipitation. Being similar to Pd(PEt3)4, 3d could also undergo hydropalladation with the combination of phenylacetylene and (EtO)2P(O)H, forming the expected vinyl-Pd-phosphoryl complex, but with a slower reaction rate. The result indicated that alkenylphosphoryl compounds generated from the palladium-catalyzed hydrophosphorylation of alkynes with H-phosphonates might play a negative role in the hydropalladation step of the catalytic cycle. Complexes 3a~3g and phosphonium 4 were charaterized by NMR analysis. The structures of 3a and 4 were also confirmed by X-ray technology.

Key words: alkenylphosphoryl compounds, group 10 transition metals, coordination compounds