Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (7): 1656-1662.DOI: 10.6023/cjoc201803015 Previous Articles     Next Articles



赵明晶a, 毛国梁a, 刘洋b, 肖洁b, 邓亮b   

  1. a 东北石油大学化学化工学院 石油与天然气化工省重点实验室 大庆 163318;
    b 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:2018-03-12 修回日期:2018-04-04 发布日期:2018-04-13
  • 通讯作者: 毛国梁, 邓亮;
  • 基金资助:


Synthesis, Structure, and Nitrene-Transfer Reactivity of High-Spin Iron(Ⅱ) Complex Featuring Iminoarsorane Ligation

Zhao Mingjinga, Mao Guolianga, Liu Yangb, Xiao Jieb, Deng Liangb   

  1. a Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318;
    b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2018-03-12 Revised:2018-04-04 Published:2018-04-13
  • Contact: 10.6023/cjoc201803015;
  • Supported by:

    Project supported by the National Key Research and Development Program of the Ministry of Science and Technology (No. 2016YFA0202900), the National Natural Science Foundation of China (Nos. 51534004, 21725104, 21690062, 21432001, U1362110) and the CAS Strategic Pilot Science and Technology Special (No. XDB20000000).

Treatment of (2,6-F2C6H3)(2-BrC6H4)NH with 2 equiv. of nBuLi, followed by the interaction with 0.5 equiv. of PhAsCl2 and quenching with aqueous solution, afforded the new bis(amido)-arsorane ligand ((o-(N-(2,6-2C6H3)NH)C6H4)2AsPh (denoted as H2(dfpN2As)). The interaction of H2(dfpN2As)) with 0.5 equiv. of[Fe(N(TMS)2)2]2 resulted in amine elimination and gave the bis(amido)-arsorene-iron(Ⅱ) complex[(κ-N,N,P-dfpN2As)Fe(THF)2] (3). Further treatment of 3 with the organic azide DippN3 rendered the formation of the first iminoarsorane-transition-metal complex[(κ-N,N,N-dfpN2AsNDipp)Fe(THF)] (4) as an air- and moisture-sensitive green solid. Reactivity study indicated that 4 can undergo nitrene-transfer reactions with excess amounts of 2,6-dimethylphenylisocyanide and PPh3 to produce the nitrene-transfer products DippNCNC6H3Me2-2,6 and Ph3PCNC6H3Me2-2,6, respectively and the corresponding bis(amido)-arsorane-iron(Ⅱ) complexes[(κ-N,N,As-dfpN2As)Fe(CNC6H3Me2-2,6)3] (5) and[(κ-N,N,As-dfpN2As)Fe(PPh3)] (6). These complexes were fully characterized by various spectroscopic methods. Solution magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy (δ=0.88 mm/s,|ΔEQ|=1.50 mm/s; δ=0.90 mm/s,|ΔEQ|=2.53 mm/s; and δ=0.65 mm/s,|ΔEQ|=2.23 mm/s for 3, 4, and 6, respectively) indicated that 3, 4 and 6 are high-spin iron(Ⅱ) complexes, whereas the well-resolved diamagnetic NMR spectra of 5 in combination with its 57Fe Mössbauer spectrum data (δ=0.05 mm/s,|ΔEQ|=0.40 mm/s) revealed its low-spin iron(Ⅱ) nature. The molecular structures of 3~5 have been characterized by single-crystal X-ray diffraction studies. The dianionic bis(amido)-arsorane ligands in 3 and 5 chelate to the metal centers in a fac-fashion with the Fe-As distances being 0.2562(3) and 0.2293(1) nm, respectively. The dianionic bis(amido)-iminoarsorane ligand in 4 binds to the iron(Ⅱ) center in a fac-fashion. The Fe-As distance (0.285 nm) observed in 4 is longer than the sum of the covalent radii of Fe and As, indicating the absence of strong Fe-As interaction in the iminoarsorane-iron(Ⅱ) complex. Its As-N distance of 0.1752(3) nm is found comparable to those of the As-N bonds in the reported iminoarsoranes and bis(arsoranylidene) ammonium compounds.






Key words: arsorane, iminoarsorane, iron, nitrene, group-transfer