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Synthesis, Isolation, and Structures of Multiple Bonded Compounds Containing Heavier Main-Group Elements

含有较重主族元素的多重键合化合物的合成、分离和结构

基本信息

批准号：
13304049
负责人：
YOSHIFUJI Masaaki
金额：
$ 35.28万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2004
项目状态：
已结题

项目摘要

Multiple bonds involving heavier main-group elements are normally unstable, because bond lengths between the two elements are long and because effective overlap of □-orbitals cannot be expected due to the wide orbital lobes. Furthermore, hybridization of orbitals is not effective in higher elements causing multiple bonds of such elements to be unstable. By introducing a very bulky group into the systems, however, we have been able to isolate unusual phosphorus-containing compounds, where the phosphorus atoms are in low coordination states.In this research project, protection groups, such as the 2,4,6-tri-t-butylphenyl group, have been utilized in the stabilization of low coordinated phosphorus compounds of coordination number 1 and 2. Compounds thus protected were isolated, characterized, and the structures were analyzed by multinuclear NMR spectroscopy and X-ray crystallography.1)Novel protection groups, which are useful in studies of substitution effects, both steric and electronic, have been developed for preparation of diphosphenes, phosphaallenes, diphosphinidenecyclobutenes, and phosphaalkynes.2)Cis-diphosphenes, phosphaallenes, thioxophosphines, and phosphaquinoid compounds were prepared and characterized by use of novel steric protection groups.3)Diphosphacyclobutenes and biradical species, diphosphacyclobutanediyls, were prepared and isolated by the reaction of phosphaalkynes with alkyllithium reagents.4)Sterically protected phosphaethenylcarbenoids were generated and the various reactivities were studied involving the formation of phosphaalkynes, diphosphabutatrienes, diphosphabutadienes, triphosphafulvenes, and diphosphafulvenes. The structures were analyzed mostly by X-ray crystallography.5)Various kinds of diphosphinidenecyclobutenes were prepared and the transition metal complexes were formed. The catalytic activities in the coupling reactions were investigated to show that they are effective catalysts.

包含较重主族元素的多重键通常是不稳定的，因为两个元素之间的键长较长，而且由于轨道叶较宽，无法预期□轨道的有效重叠。此外，轨道的杂化在更高的元素中是无效的，导致这些元素的多重键不稳定。通过引入一个非常庞大的基团到系统中，然而，我们已经能够分离出不寻常的含磷化合物，其中磷原子处于低配位状态。在本研究项目中，保护基团，如2，4，6-三叔丁基苯基，已被用于稳定低配位磷化合物的配位数1和2。2）顺式二膦、磷丙二烯、硫代膦、硫代和磷醌类化合物的制备和表征。3）二磷杂环丁烯和双自由基物质，二磷杂环丁烷二基，通过磷炔与烷基锂试剂的反应制备和分离。4）空间保护的phosphaethenylcarbenoids产生和各种反应性进行了研究，涉及形成的phosphaalkynes，diphosphabutatrienes，diphosphabutadienes，triphosphafulvenes，和diphosphafulvenes。5）合成了多种双膦杂环丁烯类化合物，并与过渡金属形成配合物。考察了它们在偶联反应中的催化活性，结果表明它们是有效的催化剂。

项目成果

期刊论文数量（143）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Studies on the Electronic Effects of Bulky Aryl Substituents on Low Coordinated Phosphorus Atoms in Diphosphenes and Phosphaalkenes by Functionalization at the Para Position

通过对位官能化研究大体积芳基取代基对双磷烯和磷烯中低配位磷原子的电子效应

DOI：
发表时间：
2005
期刊：
Bulletin of the Chemical Society of Japan 78(印刷中)
影响因子：
0
作者：
H.Tsukamoto;M.Sato;Y.Kondo;Akitake Nakamura;Anil S.Gajare;Subaru Kawasaki;Subaru Kawasaki;Akitake Nakamura;Subaru Kawasaki;Rader S.Jensen;小澤文幸;Subaru Kawasaki;Subaru Kawasaki
通讯作者：
Subaru Kawasaki

Monochalcogenization of a Sterically Encumbered 1,4-Diphosphafulvene

空间阻碍的 1,4-二磷富烯的单硫属化