有机化学 ›› 2024, Vol. 44 ›› Issue (1): 173-179.DOI: 10.6023/cjoc202308002 上一篇    下一篇

研究论文

含不同取代基的钌-锗化合物的合成及表征

田雁, 董睿, 聂鹏*(), 许波   

  1. 贵州省食品药品检验所 贵阳 550004
  • 收稿日期:2023-08-02 修回日期:2023-09-14 发布日期:2023-09-21
  • 基金资助:
    贵州省科技厅基金(黔科合基础-ZK[2021]一般041)

Synthesis and Characterization of Ruthenium Germyl Complexes with Various Substituents

Yan Tian, Rui Dong, Peng Nie(), Bo Xu   

  1. Guizhou Institute for Food and Drug Control, Guiyang 550004
  • Received:2023-08-02 Revised:2023-09-14 Published:2023-09-21
  • Contact: *E-mail: niepeng2001@163.com
  • Supported by:
    Guizhou Provincial Science and Technology Agency Project(No. Qian Ke He Basic-ZK[2021]General 041)

钌-锗化合物(PPh3)(X)RuGeCl2ArTrip (X=H, 1; Cl, 2; ArTrip=C6H3-2-(η6-Trip)-6-Trip, Trip=2,4,6-iPr3-C6H3)与有机试剂如格氏试剂、LiHBEt3以及萘钠反应实现了锗和钌原子上的取代基团的调控. 化合物1与格氏试剂EtMgBr在不同的温度下反应, 分别生成(PPh3)HRuGeBr2ArTrip (3)和(PPh3)HRuGeEt2ArTrip (4). 化合物1和LiHBEt3反应也生成化合物4, 在该反应中LiHBEt3作为乙基转移试剂而不是氢化试剂. 此外, 化合物1与HBF4反应生成离子型化合物[(PPh3)H2RuGeCl2ArTrip][BF4] (5). 另外, 利用Na/naphthalene还原化合物2可以得到双羟基化合物(PPh3)HRuGe(OH)2- ArTrip (6), 而化合物2与碘单质的反应历经单碘化, 形成化合物(PPh3)IRuGeCl2ArTrip (7). 所有的化合物都经过详细的核磁谱学和X射线单晶衍射的表征.

关键词: 钌, 锗宾, 取代反应, 结构

Reactions of dichlorogermyl ruthenium complexes (PPh3)(X)RuGeCl2ArTrip (X=H, 1; Cl, 2; ArTrip=C6H3-2- (η6-Trip)-6-Trip, Trip=2,4,6-iPr3-C6H3) with various reagents, including Grignard reagent, LiHBEt3 and Na/naphthalene were investigated, realizing the substituent modulation on Ge and Ru atoms. 1 reacted with EtMgBr forming (PPh3)HRu- GeBr2ArTrip (3) and (PPh3)HRuGeEt2ArTrip (4) depending on the reaction temperature. The reaction of 1 with LiHBEt3 also resulted in the formation of 4, where LiHBEt3 acted as ethyl transfer reagent instead of hydrogenation reagent. Additionally, 1 reacted with HBF4 afforded ionic product [(PPh3)H2RuGeCl2ArTrip][BF4] (5). On the other hand, reduction of 2 with Na/naphthalene produced dihydroxyl complex (PPh3)HRuGe(OH)2ArTrip (6), while the reaction with I2 underwent monoiodination on Ru with the formation of (PPh3)IRuGeCl2ArTrip (7). All compounds were fully characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction.

Key words: ruthenium, germylene, substitution, structure