Studies on the Establishment of the Central Dogma for Heteroatom Chemistry

杂原子化学中心法则建立的研究

• 批准号: 06303002
• 负责人: FURUKAWA Naomichi
• 金额: $ 6.91万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Co-operative Research (A)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06303002/
• 关键词: Heteroatom compound; Central Dogma; Low coodinate bond; Bulky substituent; High coodinate bond; Higher periodic compound; Pseudo rotation; Active species; ヘテロ原子間結合; 高配位化合物; 擬回転; 配位子カップリング反応; 多種結合化合物; カチオンラジカル; ジカチオン

The purpose of this research intended to manifest the concepts to be commonly applied for the chemical-bondings of the organo-heteroatom compounds (the elements belonging to the groups 14 to 17 in the periodic table) and also establish the commonly acceptable concepts called the new "central dogma" by elucidating the nature of the chemical bondings in the heteroatom chemistry. Major results obtained are in the following, 1) Theoretical MO-calculations of the bondings involving the Si derivatives revealed their characteristic properties. In the case of groups 15 and 16 elements, those belonging to the higher periodic derivatives are stabilized more and by the development of the theoretical and experimetal studies, molecular designs, synthesis, and structural determination have become possible. The detailed experiments on the pseudo-rotation and ligand-coupling reactions of the compounds of groups 15 and 16 elements have been undergone. 2) The multiple-bonds in the Si and P compounds are stabilized both by the bulky and electron-rich substituents attached to the central elements. Furthermore, polysilicon compounds such as two- and three dimensional and highly strained molecules have been synthesized. 3) Organic synthesis and generation of active species using the high-coordinate compounds belonging to groups 15-17 have been tried and these investigations successfully developed the field of heteroatom compounds

本研究的目的是阐明通常应用于有机杂原子化合物（属于元素周期表中第 14 至 17 族的元素）化学键的概念，并建立普遍接受的概念，称为“新化学键”。通过阐明杂原子化学中化学键的性质来理解“中心法则”。获得的主要结果如下：1）涉及Si衍生物的键的理论MO计算揭示了它们的特性。就第 15 族和第 16 族元素而言，属于较高周期衍生物的元素更加稳定，并且通过理论和实验研究的发展，分子设计、合成和结构测定已成为可能。对15族和16族元素化合物的拟旋转和配体偶联反应进行了详细的实验。 2）Si和P化合物中的多重键通过连接到中心元素的大体积且富含电子的取代基来稳定。此外，还合成了多晶硅化合物，例如二维和三维以及高应变分子。 3）尝试了使用属于15-17族的高配位化合物进行有机合成和活性物种的生成，这些研究成功开拓了杂原子化合物领域

项目成果

Ryu Sato: "First Systematic Synthesis and Electrochemical Oxidation of 4,7-Disopropyl-1,2,3-benzotrichalcogenoles Containing Both Sulfer and Selenium Atoms" Tetrahedron Letters. 35. 5469-5472 (1994)

Ryu Sato：“首次系统合成和电化学氧化含有硫和硒原子的 4,7-二异丙基-1,2,3-苯并三卤代烷醇”四面体快报。

岡崎廉治: "Synthesis,Structure,and Thermolysis of a Tetracoordinate 1,2λ^4-Oxathietane" Angewandte Chemie. 33. 2094-2095 (1994)

Renji Okazaki：“四配位 1,2λ^4-Oxathietane 的合成、结构和热解”Angewandte Chemie。33。2094-2095 (1994)

Masaaki Yoshifuji: "Preparation and Structure of Dichloropalladium(II)Complexes of Sterically Protected Diphosphinidenecvclobutenes and Their Synthetic Application as Homogeneous Catalyst" Chemistry Letters. 221-222 (1995)

Masaaki Yoshifuji：“空间保护的二膦酰氯丁烯二氯钯(II)配合物的制备和结构及其作为均相催化剂的合成应用”化学快报。

吉藤正明: "2,4-di-t-butyl-6-methoxyphenyldithioxophosphorane as a Probe for the Mechanistic Studies of Lawesson's Reagent" Tetrahedron Letters. 35. 4379-4382 (1994)

Masaaki Yoshifuji：“2,4-二叔丁基-6-甲氧基苯基二硫代正膦作为劳森试剂机理研究的探针”四面体快报 35。4379-4382 (1994)

Kohei Tamao: "Remarkably Facile Thermal Generation of Silylene from a Pentacoodinate Alkoxydisilane and Its Trapping as a Pentacoordinate 1,2-Disilacyclobut-3-ene" J.Am.Chem.Soc.117. 11592-11593 (1995)

Kohei Tamao：“从五配位烷氧基二硅烷中非常容易地热生成硅烯及其作为五配位 1,2-二硅杂环丁-3-烯的捕获”J.Am.Chem.Soc.117。