Construction of Hypervalent Organometalloidal Systems in Main-group Elements and Exploration of their New Reactions

1.类金属主族元素(锡、锑、铋等)的各种高价化合物都是通过使用特殊设计的双齿配体(马丁配体)合成的。研究了高价锑化合物(10-Sb-5)与有机锂或格氏试剂反应生成相应的络合物(12-Sb-6，12-Bi6)的卤代反应。根据光谱数据确定了ATE络合物(12-Sb-6)的结构及其异构化机理。2)合成了稳定的铋(12-Bi-6)ATE络合物，并研究了其化学行为。3)合成了几种锡(10-Sn5)的ATE络合物，并根据核磁共振波谱特征确定了它们的结构。通过一种新型的三齿配体，合成了多种含锑或铋原子的偶氮碱衍生物。1)在N-甲基核磁共振化学位移的Hammett线性关系的基础上，研究了跨环超价相互作用和键的形成。Sigma m取代基常数2)讨论了主族元素周围稳定几何构型的异构化，并对铋化合物的还原消除进行了研究。

1. Various hypervalent compounds of metalloidal main-group elements (Sn, Sb, Bi etc.) were synthesized by using a specially designed bidentate ligand (Martin's ligand). Treatment of these hypervalent compounds with organolithiums or Grignard reagents converted then into the corresponding ate complexes (12-Sb-6, 12-Bi-6).1) Halogenation,of the hypervalent antimony compounds (10-Sb-5) was investigated. Structure of ate complexes (12-Sb-6) and their isomerization mechanism were determined on the basis of spectral data.2) A stable ate complex of bismuth (12-Bi-6) was prepared and its chemical behaviors were investigated.3) Some ate complexes of tin (10-Sn-5) were prepared and their structure was clarified according to the NMR spectrum features.2. Various azocine derivatives containing antimony or bismuth atom were synthesized by means of a new type tridentate ligand.1) Transannular hypervalent interaction and bond formation was investigated on the basis of Hammett's linear relationship in NMR chemical shift of N-methyl group using. sigma m substituent constants.2) Isomerization of stable geometry around main-group elements was discussed and reductive elimination in bismuth compounds was also studied.