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

1.类金属主族元素（Sn、Sb、Bi等）的各种高价化合物通过使用特别设计的双齿配体（马丁配体）合成。用有机锂或Grignard试剂处理这些高价锑化合物，然后转化成相应的酯配合物（12-Sb-6，12-Bi-6）。1）研究了高价锑化合物（10-Sb-5）的卤化。合成了稳定的铋（12-Bi-6）配合物，并对其化学行为进行了研究; 3）合成了锡（10-Sn-5）配合物，并根据核磁共振谱特征确定了配合物的结构.利用一种新型的三齿配体，合成了多种含锑或铋原子的吖辛因衍生物。1）利用N-甲基NMR化学位移的Hammett线性关系，研究了跨环超价相互作用和成键。σ m取代基常数。2）讨论了铋化合物中主族元素周围稳定几何构型的异构化，并研究了铋化合物中的还原消除。

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.