Investigation of Common Character in Reactions of Hetero Atoms and Organometallics

1.为了研究硅、硫、硒、碲、磷、锑等新的、有趣的杂原子有机化合物的性质，合成了一系列新型的含杂原子有机化合物，发现了一些硅化合物中存在着很强的&lt；sigma&gt；/&lt；pi&gt；一些低配位的磷化合物是在空间保护官能团的基础上合成的，它们具有不同寻常的化学行为。高价化合物(硫烷、磷烷、茂硼烷等)是由五元配体形成的。许多含杂原子的小环化合物也得到了积极的研究。在硒存在下，胺和一氧化碳发生催化反应生成尿素。用碲化钠或三芳基锑进行了有机化合物的脱溴反应，并对其反应机理进行了探讨。1，2-立体专一性反应设计为片呐醇类型重排，与…烷基铝试剂较多。在有机过渡金属钴、钯、钚、锆等催化剂上进行了多种合成反应，包括官能团之间的相互转化、杂环的合成、一氧化碳的插入以及金属-二烯配合物的扩环反应。新设计的配体，如卟啉、膦和大环多胺，发展了一些有趣的光反应、有用的不对称反应和新的功能。此外，设计合成了高自旋有机分子，并对其磁性进行了研究。从反应机理的角度讨论了杂环化合物中的取代基效应、有机化合物中的溶质-溶剂相互作用以及杂原子参与的自由基的物理化学行为。用X-射线晶体分析确定了部分有机硫化合物的超价结构。从理论上解释了经典的氧化数概念。用从头算方法从理论上确定了前所未有的含杂原子的分子和活性中间体的结构和相对稳定性。较少

1. Various novel organic compounds containing hetero atoms were synthesized in order to investigate new and interesting properties which can be ascribed to the hetero atom such as silicon, sulfur, selenium, tellurium, phosphorus, antimony and etc. There were found evidence for a strong <sigma> / <pi> interaction in some silicon compounds. Some lower coordinated phosphorus compounds were prepared on the basis of sterically protected functionality and they have unusual chemical behaviors. Hypervalent compounds (sulfurane, phosphorane, stiborane, etc.) were formed by means of five-membered ligands. Many small ring compounds containing hetero atoms were also studied vigorously. A catalytic reaction from amine and carbon monoxide into urea occurred in the presence of selenium. Debromination of organic compounds was developed by using sodium telluride or triarylstibine and their reaction mechanisms were clarified. 1,2-Stereospecific reactions were designed in pinacol type rearrangement with … More alkyl aluminum reagents.2. Several synthetic reactions were developed by means of organo transition metal catalysts such as cobalt, paradium, ruthenium, zirconium and etc. There were interconversion between functional groups, synthesis of heterocycles, insersion of carbon monoxide, and ring-expansion of metal-diene complexes. New design of ligand such as porphyrin, phosphine, and macrocyclic polyamine developed some interesting photoreactions, useful asymmetric reactions, and novel functions. Furthermore, high-spin organic molecules were designed and synthesized and their magnetic behaviors were studied.3. Substituent effects in heterocyclic compounds, solute-solvent interactrions in organic compounds, and physicochemical behaviors of radicals participated with hetero atoms were discussed from standpoint of reaction mechanism. Hypervalent structure of some organic sulfur compounds was confirmed by means of X-ray crystal analysis. The classical concept of the oxidation number was interpreted theoretically. Structure and relative stability of unprecedented molecules and reactive intermediates containing hetero atoms were determined theoretically with ab initio calculation. Less