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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