有机化学 上一篇    下一篇

研究论文

新型取代基炔类分子的合成及其与B(C6F5)3的反应

席鑫, 张公平, 李建成, 黄艳婷, 蒋文军, 吴鹏, 朱红平   

  1. 固体表面物理化学国家重点实验室,厦门大学化学化工学院 厦门 361005
  • 收稿日期:2020-07-06 修回日期:2020-08-17 出版日期:2030-01-01 发布日期:2020-09-16
  • 通讯作者: 朱红平 E-mail:hpzhu@xmu.edu.cn
  • 基金资助:
    国家自然科学基金面上项目21972112和21673191.

Synthesis of Alkynes Composed of the Novel Substituents and their Reactions with B(C6F5)3

Xin Xi, Gongping Zhang, Jiancheng Li, Yanting Huang, Wenjun Jiang, Peng Wu, Hongping Zhu   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005
  • Received:2020-07-06 Revised:2020-08-17 Online:2030-01-01 Published:2020-09-16
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21673191 and 21972112).

本工作合成了5种不同取代基的炔类化合物Mes2HSiC≡CPh(1,Mes=2,4,6-Me3C6H2)、[tBuC (NAr)2]GeC≡CPh(2,Ar=2,6-iPr2C6H3)、[PhC (NtBu)2]SnC≡CPPh23)、[HC (CMe)2(NAr)2]SnC≡CPPh24)和[HC (CMe)2(NAr)2]ZnC≡CPPh25),研究了这些化合物与B (C6F53的反应。在与B (C6F53的反应中,12均发生1,1-碳硼化反应生成烯烃化合物(Ph) Mes2HSiC=C (C6F5) B (C6F526)和{[tBuC (NAr)2]Ge}(Ph) C=C (C6F5) B (C6F527),7是一种GeII/B松散Lewis酸碱对化合物;35则都发生B (C6F53与配体金属基的位置交换、进而配体金属基转换键合PPh2的反应,分别生成新颖的分子内双性离子炔烃化合物[PhC (NtBu)2]SnP (Ph2) C≡CB (C6F538)、[HC (CMe)2(NAr)2]SnP (Ph2) C≡CB (C6F539)、[HC (CMe)2(NAr)2]ZnP (Ph2) C≡CB (C6F5310)。文中还讨论了反应机理。

关键词: 新型取代基炔烃, B (C6F5)3, 1,1-碳硼化反应, 基团转换反应, 新型取代基烯烃

Five alkyne compounds of varied novel substituents as Mes2HSiC≡CPh (1, Mes=2,4,6-Me3C6H2), [tBuC(NAr)2]GeC≡CPh (2, Ar= 2,6-iPr2C6H3),[PhC(NtBu)2]SnC≡CPPh2 (3),[HC(CMe)2(NAr)2]SnC≡CPPh2, (4) and[HC(CMe)2(NAr)2]ZnC≡CPPh2 (5) have been synthesized. Compounds 1 and 2 each reacted with B(C6F5)3 by the 1,1-carboboration to give compounds (Ph)Mes2HSiC=C(C6F5)B(C6F5)2 (6) and {[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7) respectively, where a (F5C6)3B/Mes2HSi group exchange was suggested to occur initially for the former reaction while the (F5C6)3B/[tBuC(NAr)2]Ge SiHMes2 exchange was for the latter one. Compound 6 is a acyclic alkene whereas 7 is viewed as a germanaboracyclobutene owing to a strong Ge→B donor-acceptor bonding being a Ge/B frustrated Lewis pair (FLP). Compounds 3-5 each reacted with B(C6F5)3 to undergo a ligand coordinated metal group/B(C6F5)3 exchange followed by bonding of the metal group at the PPh2, resulting in formation of a novel type of the intramolecular zwitterionic alkynes[PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3 (8),[HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3 (9), and[HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10), respectively. Compounds 1-10 have all been characterized by spectroscopy and elemental analysis, of which 4, 6, 7, and 10 are further authenticated by X-ray crystallography. The mechanisms of these reactions are discussed.

Key words: alkynes of novel substituents, B (C6F5)3, 1,1-carboboration, group exchange reaction, alkenes of novel substituents