Syntheses of Polymers of Bidentate Ligands Containing Phosphorus-Carbon Double Bonds

含磷碳双键双齿配体聚合物的合成

基本信息

批准号：
13640522
负责人：
TOYOTA Kozo
金额：
$ 1.92万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640522/
关键词：
Heavier Main Group Element Heteroatom Chemistry Low Coordinated Phosphorus Compound Steric Protection Kinetic Stabilization Transition Metal Complex Complex Catalyst Polymer Material

项目摘要

Various polymers of sterically protected 3,4-diphosphinidenecyclobutenes, which are unique bidentate ligands having phosphorus-carbon double bonds, were prepared and their properties were studied. For example, a new sterically protected 3,4-diphosphinidenecyclobutene, containing 4-(4-vinylphenyl)butyl group at the 1- and 2-positions, was prepared and converted to a polymer. In the successive reaction of bis[(2,4,6-tri-t-butylphenyl)phosphino]diynes with t-butyllithium and 1,2-dibromoethane, 3,4-diphosphinidenecyclobutene derivatives having ring-fused structures were obtained as major products along with diphosphinidenecyclobutene polymers. Sterically protected 3,4-diphosphinidene-1,2-dithienylcyclobutenes were also prepared and converted to polymers and/or oligomers, via functionalization of the thienyl moieties. Some polymers and oligomers, as well as their monomers, were allowed to react with bis(acetonitrile)dichloropalladium or bis(acetonitrile)dichloroplatinum to give metal comple … More xes of the bidentate ligands. Structures of some diphosphinidenecyclobutene monomers and their transition metal complexes were analyzed by X-ray crystallography. A relatively large geometrical change induced by the complex formation was exhibited in the case of 3,4-diphosphinidenecyclobutenes having ring-fused structures.Moreover, some new sterically protecting groups were developed. A sterically protecting auxiliary of the metacyclophane type was newly developed and applied to preparations of unsymmetrically substituted diphosphene and 1,3-diphosphaallene. Unsymmetrical 1,4-diphosphabutatriene was prepared for the first time, using the sterically protecting group of metacyclophane type, and the properties were studied. Sterically hindered aryl substituents having an electron-donating group at the o- or p-positions, were also developed. Thus, 2,4-di-t-butyl-6-(phenoxymethyl)phenyl group and 2,6-di-t-butyl-4-methoxyphenyl group were developed and the substituents were applied to preparations of diphosphenes as well as dichlorophosphines and fluorenylidenepbosphines. Structures of some low coordinated phosphorus compounds bearing the electron-donating sterically demanding groups were studied by X-ray crystallography and the effect of the substituents were discussed. Less

制备了各种空间保护的3,4-二膦亚膦环丁烯聚合物，并研究了它们的性能，例如，含有4-(的新型空间保护的3,4-二膦亚膦环丁烯。 1-位和2-位的4-乙烯基苯基)丁基在以下连续反应中制备并转化为聚合物。与叔丁基锂和1,2-二溴乙烷形成的双[(2,4,6-三叔丁基苯基)膦基]二炔得到的具有环稠合结构的3,4-二亚膦环丁烯衍生物与二亚膦环丁烯一起作为主要产物空间保护的聚合物。还制备了3,4-二膦基-1,2-二噻吩基环丁烯，并通过噻吩基部分的官能化将一些聚合物和低聚物及其单体与双(乙腈)反应转化为聚合物和/或低聚物。二氯钯或双(乙腈)二氯铂可提供金属络合物……更多双齿化合物的xes通过X射线晶体学分析了一些二膦亚基环丁烯单体及其过渡金属配合物的结构，在具有环稠合结构的3,4-二膦亚基环丁烯的情况下，表现出由配合物形成引起的相对较大的几何变化。，开发了一些新的空间保护基团，新开发了间环芬型空间保护助剂，并将其应用于不对称制剂的制备。首次利用间环芳型空间保护基团制备了不对称的1,4-二磷杂环烯，并研究了邻位具有给电子基团的空间位阻芳基取代基的性质。 - 或 p-位置，因此也被开发出来。开发了2,4-二叔丁基-6-(苯氧基甲基)苯基和2,6-二叔丁基-4-甲氧基苯基，并将这些取代基应用于二膦、二氯膦、亚芴基苯膦的制备。通过X射线晶体学和方法研究了一些低配位含磷化合物的结构以及供电子空间需求基团取代基的影响讨论较少。