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

制备了具有磷的独特的三磷酸烯烃的各种聚合物，它们是具有磷碳双键的独特鸟酸配体，并进行了研究。例如，制备了一种新的在1和2位置的新型静脉保护的3,4-二磷酸二环丁烯，其中包含4-（4-乙烯基苯基）丁基基团，并转换为聚合物。在BIS [（2,4,6-Tri-T-T-叔丁基苯基）磷酸的成功反应中，Diynes与T-丁基乙烷和1,2-二溴乙烷，3,4-二磷酸二甲基丁烯衍生物具有带环融合结构的结构，并作为主要产物与双磷酸二甲基丙烯酸酯polyclyclobutenemerss一起获得。通过硫烯基部分的功能化，还制备了经空间保护的3,4-二磷酸1,2-二苯基环霉丁烯并转化为聚合物和/或低聚物。聚合物和低聚物及其单体被允许与双（乙腈）二氯丙酰胺或二氯二氯丙氨酸的二氯苯二甲酸反应，以使金属完整……更多的鸟类配体的XES。通过X射线晶体学分析了一些二磷酸烯烃单体及其过渡金属复合物的结构。在3,4-二磷酸化的环胞环烯烯具有带环融合的结构的情况下，暴露了复合物形成引起的相对较大的几何变化。此外，开发了一些新的空间保护组。新开发的元环磷型辅助机构的空间保护辅助机构，并应用于未取代的双磷酸和1,3-二磷酸的制剂中。首次使用元眼素类型的静脉保护组，第一次制备了不对称的1,4-二磷酸二磷酸酯，并且这些特性是研究的。还开发了在O-或p位置具有电子含量组的阻碍芳基亚探测器。开发了2,4-二-DI-T-叔丁基-6-（苯氧甲基）苯基和2,6-二二丁基-4-甲基苯基基团，并将亚列用于二磷蛋白以及二氯磷酸和氟苯基肾上腺素的制剂。通过X射线晶体学研究了一些含有电子含量的含电子含量的磷的磷的结构，并讨论了亚t仪的效果。较少的