Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (10): 3380-3389.DOI: 10.6023/cjoc202005089 Previous Articles     Next Articles


刘健, 肖洁, Sudipta Mondal, 冷雪冰, 邓亮   

  1. 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032
  • 收稿日期:2020-05-29 修回日期:2020-06-27 发布日期:2020-07-01
  • 通讯作者: 邓亮
  • 基金资助:

Reactions of Iron(II) Complexes Supported by Tripodal Amido-Phosphine-Amido Ligands with Diazo Compounds

Liu Jian, Xiao Jie, Mondal Sudipta, Leng Xuebing, Deng Liang   

  1. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2020-05-29 Revised:2020-06-27 Published:2020-07-01
  • Supported by:
    Project supported by the National Key Research and Development Program of the Ministry of Science and Technology (No. 2016YFA0202900), the Natural Science Foundation of China (Nos. 21725104, 21690062, 21821002), CAS Strategic Pilot Science And Technology Special (No. XDB20000000), and the Program of Shanghai Academic Research Leader (No. 19XD1424800).

Treatment of ButPCl2 with 2 equiv. of (2,4,6-Me3C6H2)(2-LiC6H4)NLi and (2,6-Cl2C6H3)(2-LiC6H4)NLi, which were generated in situ by the interaction of (2,4,6-Me3C6H2)(2-BrC6H4)NH and (2,6-Cl2C6H3)(2-BrC6H4)NH with 2 equiv. of BunLi, followed by quenching with water, afforded new tridentate diamine-phosphine compounds (o-(N-(2,4,6-Me3C6H2)-NH)C6H4)2PBut and (o-(N-(2,6-Cl2C6H3)NH)C6H4)2PBut (denoted as H2(MesN2PBu-t) and H2(dcpN2PBu-t)), respectively. H2(MesN2PBu-t) and H2(dcpN2PBu-t) underwent amine-elimination reaction with[Fe(N(SiMe3)2)2]2 (0.5 equiv.) to afford iron(Ⅱ) complexes[(κ3-N,N,P-MesN2PBu-t)Fe(OEt2)] (1) and[(κ3-N,N,P-dcpN2PBu-t)Fe(OEt2)] (2) bearing tridentate diamido-phosphine ligands. Treatment of 1 with organic diazo compounds (p-tolyl)2CN2 and PhC(N2)CO2Et rendered the formation of diazo coordinated iron complexes[(κ3-N,N,P-MesN2PBu-t)Fe(η2-N,N-(p-tolyl)2CN2)] (3) and[(κ3-N,N,P-MesN2PBu-t)Fe(κ2-N,O-PhC(N2)- CO2Et)] (4), respectively. Complex 2 can catalyze the conversion of (p-tolyl)2CN2 to (p-tolyl)2C=NN=C(tolyl-p)2. Treatment of 2 with organic diazo compound DmpC(N2)H rendered the formation of a high-spin iron(Ⅱ) complex featuring the tridentate bisamido-phosphine ylide ligand[(κ3-N,N,C-dcpN2PBu-tCH,Dmp)Fe] (5). These complexes have been characterized by elemental analysis, 1H NMR, solution magnetic susceptibility measurements, zero-field 57Fe Mössbauer spectroscopy and single-crystal X-ray diffraction studies. The spectroscopic data in combination with theoretical study suggest that complex 3 can be viewed as a low-spin iron(IV) imido complex featuring an dianionic ligand[η2-N,N-(p-tolyl)2CN2]2-, whereas 4 has an intermediate-spin iron(Ⅲ) center that is antiferromagnetically coupled to a diazoalkane radical anion[κ2-N,O-PhC(N2)-CO2Et)]•1-.

Key words: iron, diazo compounds, diamido-phosphine ligand