Copsey May C, Gallon Sabrina B, Grocott Sara K, Jeffery John C, Russell Christopher A, Slattery John M
School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, U.K.
Inorg Chem. 2005 Jul 25;44(15):5495-500. doi: 10.1021/ic050127v.
High-yielding syntheses of complexes based around the cyclodistibazane (Sb(2)N(2)) core are described from the reaction of organoantimony(V) chlorides with varying stoichiometric amounts of lithiated primary amines, LiN(H)R. Thus, mixing Ph(3)SbCl(2) with 2 equiv of LiN(H)R (R = CH(2)Ph) produces Ph(3)Sb(mu-NR)(2)SbPh(3) (1). Mixed amido/imido complexes of formula {R(H)N}Ph(2)Sb(mu-NR)(2)SbPh(2){N(H)R} (2) (R = CH(2)Ph, 2-OMe-5-(t)()Bu-C(6)H(3), and Cy) are made from the corresponding 3:1 molar ratio combination of LiN(H)R with Ph(2)SbCl(3). A similar reaction employing only 2 equiv of LiN(H)R (R = CH(2)Ph) with 1 equiv of Ph(2)SbCl(3) yields ClPh(2)Sb(mu-NR)(2)SbPh(2)Cl (3). Compounds 2a-c and 3 possess reactive functionality which may make them useful synthetic reagents in the preparation of more complex main group imido architectures. All of the complexes have been characterized by (1)H NMR spectroscopy, elemental analysis (CHN), and X-ray crystallography. An investigation of all known crystallographically characterized Sb-N fragments from the Cambridge Structural Database highlights a series of parameters that appear to influence the observed Sb-N bond lengths.
本文描述了基于环二锑氮烷（Sb₂N₂）核心的配合物的高产率合成方法，该方法是通过有机锑（V）氯化物与不同化学计量比的锂化伯胺LiN(H)R反应实现的。因此，将Ph₃SbCl₂与2当量的LiN(H)R（R = CH₂Ph）混合可生成Ph₃Sb(μ-NR)₂SbPh₃（1）。式为{R(H)N}Ph₂Sb(μ-NR)₂SbPh₂{N(H)R}（2）（R = CH₂Ph、2-OMe-5-(t)Bu-C₆H₃和Cy）的混合酰胺/亚胺配合物是由LiN(H)R与Ph₂SbCl₃按相应的3:1摩尔比组合制备而成。使用仅2当量的LiN(H)R（R = CH₂Ph）与1当量的Ph₂SbCl₃进行类似反应，得到ClPh₂Sb(μ-NR)₂SbPh₂Cl（3）。化合物2a - c和3具有反应活性官能团，这可能使它们在制备更复杂的主族亚胺结构时成为有用的合成试剂。所有配合物均通过¹H NMR光谱、元素分析（CHN）和X射线晶体学进行了表征。对剑桥结构数据库中所有已知晶体学表征的Sb - N片段的研究突出了一系列似乎影响观察到的Sb - N键长的参数。
