含二胺基-锑配体的高自旋亚铁配合物:合成、表征及其与有机叠氮和重氮化合物的反应

doi:10.6023/cjoc201904040

有机化学 ›› 2019, Vol. 39 ›› Issue (8): 2243-2250.DOI: 10.6023/cjoc201904040 上一篇下一篇

所属专题：陈茹玉先生诞辰100周年

研究论文

含二胺基-锑配体的高自旋亚铁配合物:合成、表征及其与有机叠氮和重氮化合物的反应

王鹏, 肖洁, 冷雪冰, 邓亮

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:2019-04-16 修回日期:2019-05-13 发布日期:2019-05-15
通讯作者: 邓亮 E-mail: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.21725104，21690062，21432001，21821002）、中国科学院先导专项（No.XDB20000000）和上海市优秀学术带头人计划（No.19XD1424800）资助项目.

A High-Spin Iron(II) Complex Supported by a Tridentate Diamido-stibine Ligand: Synthesis, Structure and Its Reactions with Organic Azides and Diazo Compounds

Wang Peng, Xiao Jie, Leng Xuebing, Deng Liang

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2019-04-16 Revised:2019-05-13 Published:2019-05-15
Contact: 10.6023/cjoc201904040 E-mail: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. 21725104, 21690062, 21432001, 21821002), the Strategic Priority Research Program of Chinese Academy of Sciences (No. XDB20000000), and the Program of Shanghai Academic Research Leader (No. 19XD1424800).

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摘要/Abstract

通过PhSbCl₂与2 equiv.2-（N-锂-N-（2'，6'-二氯苯基）胺基）苯基锂的反应合成了二（2-（N-（2'，6'-二氯苯基）胺基）苯基）苯基锑[H₂（^dcpN₂Sb）].利用H₂（^dcpN₂Sb）与[Fe（N（SiMe₃）₂）₂]₂的胺消除反应合成得到二胺基-锑配位的亚铁配合物[（κ³- N，N，Sb-^dcpN₂Sb）Fe（THF）]（1）.配合物1为首例高自旋型有机锑-铁配合物.配合物1与有机叠氮化合物RN₃ [R＝dcp（2，6-Cl₂C₆H₃）]，Dipp（2，6-ⁱPr₂C₆H₃））反应生成二胺基-锑亚胺配位的亚铁配合物[（κ³-N，N，N-^dcpN₂SbN^R）Fe（py）]（R＝dcp，2；R＝Dipp，3）.配合物1与重氮化合物反应生成二胺基-锑叶立德配位的亚铁配合物[（κ³-N，N，C-^dcpN₂SbC^R1，R2）Fe（PMe₃）]（R¹＝H，R²＝CO₂Bu^t，4；R¹＝Ph，R²＝CO₂Et，5）.锑配体H₂（^dcpN₂Sb）和配合物1～5经元素分析、¹H NMR、溶液相磁化率、单晶X射线衍射等进行了表征.

关键词: 锑, 铁, 亚胺, 叶立德, 高自旋

Treatment of PhSbCl₂ with 2 equiv. of (2,6-Cl₂C₆H₃)(2-LiC₆H₄)NLi, which was generated in situ by the interaction of (2,6-Cl₂C₆H₃)(2-BrC₆H₄)NH with 2 equiv. of BuⁿLi, followed by quenching with water, afforded the diamine-stibine compound ((o-(N-(2,6-Cl₂C₆H₃)NH)C₆H₄)₂SbPh (denoted as H₂(^dcpN₂Sb)). H₂(^dcpN₂Sb) undergoes amine-elimination reaction with[Fe(N(SiMe₃)₂)₂]₂ (0.5 euiqv.) to afford an iron(Ⅱ) complex[(κ³-N,N,Sb-^dcpN₂Sb)Fe(THF)] (1) bearing an unique tridentate bisamido-stibine ligand. Solution magnetic susceptibility measurements (μ_eff=4.7(2) μ_B in C₆D₆) reveal a high spin (S=2) electronic structure for 1. Complex 1 represents the first high-spin iron(Ⅱ) complex with organic stibine ligation, and features a long Fe-Sb bond distance of 0.2792(1) nm. Density functional theory (DFT) calculations indicate weak σ interaction betwen the high-spin iron(Ⅱ) center and the antimony atom due to ineffective orbital overlap. Complex 1 can react with organic azides RN₃ to furnish the high-spin (S=2) iron(Ⅱ) complexes that bear tridentate bisamido-stibonium imine ligands[(κ³-N,N,N-^dcpN₂SbN^R)Fe(py)] (R=dcp (2,6-Cl₂C₆H₃), 2; R=Dipp (2,6-ⁱPr₂C₆H₃), 3). These compexes are among the rare metal complexes with stibonium imine ligation. The average Sb-N distance of 0.194 nm in the imine moieties is found comparable to those of the Sb-N bonds in the reported stibonium imine compounds Mes₃SbNCOCl₃ (0.199 nm) and 2-MeC₆H₄)₃SbNSO₂CF₃ (0.196 nm). The reactions of 1 with diazo compounds (R¹R²)CN₂ afford the high-spin iron(Ⅱ) complexes featuring tridentate bisamido-stibonium ylide ligands[(κ³-N,N,C-^dcpN₂SbC^R1,R2)Fe(PMe₃)] (R¹=H, R²=CO₂Bu^t, 4; R¹=Ph, R²=CO₂Et, 5). The average Sb-C distance of 0.206 nm in the ylide moieties is found comparable to those of the Sb-C bonds in the reported stibonium ylide compounds (around 0.20 nm). H₂(^dcpN₂Sb) and 1~5 have been characterized by elemental analysis, ¹H NMR, solution magnetic susceptibility measurements and single-crystal X-ray diffraction studies.

Key words: antimony, iron, imine, ylide, high-spin

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王鹏, 肖洁, 冷雪冰, 邓亮. 含二胺基-锑配体的高自旋亚铁配合物:合成、表征及其与有机叠氮和重氮化合物的反应[J]. 有机化学, 2019, 39(8): 2243-2250.

Wang Peng, Xiao Jie, Leng Xuebing, Deng Liang. A High-Spin Iron(II) Complex Supported by a Tridentate Diamido-stibine Ligand: Synthesis, Structure and Its Reactions with Organic Azides and Diazo Compounds[J]. Chin. J. Org. Chem., 2019, 39(8): 2243-2250.

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含二胺基-锑配体的高自旋亚铁配合物:合成、表征及其与有机叠氮和重氮化合物的反应

A High-Spin Iron(II) Complex Supported by a Tridentate Diamido-stibine Ligand: Synthesis, Structure and Its Reactions with Organic Azides and Diazo Compounds

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