Citation: Zhao Mingjing, Mao Guoliang, Liu Yang, Xiao Jie, Deng Liang. Synthesis, Structure, and Nitrene-Transfer Reactivity of High-Spin Iron(Ⅱ) Complex Featuring Iminoarsorane Ligation[J]. Chinese Journal of Organic Chemistry, ;2018, 38(7): 1656-1662. doi: 10.6023/cjoc201803015 shu

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

Zhao Mingjing ^a ,
Mao Guoliang ^a,, ,
Liu Yang ^b ,
Xiao Jie ^b ,
Deng Liang ^b,,

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

Corresponding author: Mao Guoliang, maoguoliang@nepu.edu.cn Deng Liang, deng@sioc.ac.cn
Received Date: 12 March 2018
Revised Date: 4 April 2018
Available Online: 13 July 2018
Fund Project: the National Natural Science Foundation of China 51534004the National Natural Science Foundation of China 21725104the National Natural Science Foundation of China 21690062Project 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)the CAS Strategic Pilot Science and Technology Special XDB20000000the National Natural Science Foundation of China U1362110the National Natural Science Foundation of China 21432001the National Key Research and Development Program of the Ministry of Science and Technology 2016YFA0202900

Figures(6)

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-^dfpN₂AsN^Dipp)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, |ΔE_Q|=1.50 mm/s; δ=0.90 mm/s, |ΔE_Q|=2.53 mm/s; and δ=0.65 mm/s, |ΔE_Q|=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, |ΔE_Q|=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.
- arsorane,
- iminoarsorane,
- iron,
- nitrene,
- group-transfer
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