砷亚胺配位的高自旋亚铁配合物的合成、表征和乃春转移反应

doi:10.6023/cjoc201803015

有机化学 ›› 2018, Vol. 38 ›› Issue (7): 1656-1662.DOI: 10.6023/cjoc201803015 上一篇下一篇

研究论文

砷亚胺配位的高自旋亚铁配合物的合成、表征和乃春转移反应

赵明晶^a, 毛国梁^a, 刘洋^b, 肖洁^b, 邓亮^b

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 E-mail:maoguoliang@nepu.edu.cn;deng@sioc.ac.cn
基金资助:
科技部国家重点研发计划（No.2016YFA0202900）、国家自然科学基金（Nos.51534004，21725104，21690062，21432001，U1362110）和中国科学院战略先导科技专项（No.XDB20000000）资助项目.

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

Received:2018-03-12 Revised:2018-04-04 Published:2018-04-13
Contact: 10.6023/cjoc201803015 E-mail:maoguoliang@nepu.edu.cn;deng@sioc.ac.cn
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).

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摘要/Abstract

通过原位形成的胺基取代苯基锂与PhAsCl₂反应合成二胺基-胂配体，并进一步由二胺基-胂配体与[Fe（N（TMS）₂）₂]₂反应合成了（二胺基-胂）亚铁配合物[（κ-N，N，As-^dfpN₂As） Fe（THF）₂]（3）.通过配合物3与有机叠氮化物DippN₃反应实现了首例砷亚胺金属配合物[（κ-N，N，N-^dfpN₂AsN^Dipp） Fe（THF）]（4）的合成.配合物4可与2，6-二甲基苯基异腈以及三苯基膦发生乃春转移反应，生成配合物[（κ-N，N，As-^dfpN₂As） Fe（CNC₆H₃Me₂-2，6）₃]（5）和[（κ-N，N，As-^dfpN₂As） Fe（PPh₃）]（6）以及相应的有机物产物DippNCNC₆H₃Me₂-2，6和Ph₃PCNC₆H₃Me₂-2，6.这些配合物通过了各种谱学手段表征，其中配合物3～5的结构还通过单晶X射线衍射得到确认.

关键词: 胂, 砷亚胺, 铁, 乃春, 基团转移

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.

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

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赵明晶, 毛国梁, 刘洋, 肖洁, 邓亮. 砷亚胺配位的高自旋亚铁配合物的合成、表征和乃春转移反应[J]. 有机化学, 2018, 38(7): 1656-1662.

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]. Chin. J. Org. Chem., 2018, 38(7): 1656-1662.

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砷亚胺配位的高自旋亚铁配合物的合成、表征和乃春转移反应

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

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