Synthesis and isolation of stable cation radicals of triarylphosphines, and development to functional molecules

三芳基膦稳定阳离子自由基的合成、分离及功能分子的开发

基本信息

批准号：
15550025
负责人：
SASAKI Shigeru
金额：
$ 2.24万
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：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

项目摘要

Crowded triarylphosphines of advanced properties were developed. One of the most crowded triarylphosphines, tris(2,4,6-tricyclohexylphenyl)phosphine was synthesized and the corresponding cation radical was prepared by oxidation with nitrosonium salts and isolated as purple crystals for the first time as a cation radical of triarylphosphine. X-ray crystallography revealed planar structure of phosphorus and anisotropic hfc constants were obtained from angular dependence of EPR spectra of a single crystal. Several crowded triarylphosphines carrying various aryl groups such as 2,6-dialkylphenyl, 2,6-diarylphenyl, and 2-alkyl-6-arylphenyl groups were synthesized and detailed structure, dynamic stereochemistry, especially inversion barrier of the phosphine and interconversion of isomers arising from helicity of propeller composed of three aromatic rings attached to the phosphorus atom. Intramolecular interaction between the crowded triarylphosphine moiety and the other functional site was also investigated. Several triarylphosphines carrying a donar or an acceptor at the 4-position to the phosphorus were synthesized and the substituent effects on electronic spectra were studied. Electron withdrawing groups such as a formyl group were found to cause red shift of the longest absorption wavelength to give orange to red colored phosphines. Crowded triarylphosphines carrying quinones were synthesized by Suzuki coupling and relation between redox properties and intramolecular charge transfer was systematically clarified. (4-Bromo-2,6-dicyclohexylphenyl)bis(2,4,6-tricyclohexylphenyl)phosphine was developed as a key synthetic intermediate for crowded triarylphosphines which can be oxidized to isolable cation radicals as well as possess functional sites. Diphosphines carrying the two crowded triarylphosphine moieties connected by biphenyl, azo, and nitroxyl linkage were synthesized.

开发了高级性质的拥挤的三磷酸。合成了最拥挤的三级膦之一，是合成的Tris（2,4,6-三环己基苯基）磷酸，并通过用硝基盐盐氧化来制备相应的阳离子自由基，并首次作为三毛磷酸的阳离子自由基氧化为紫色晶体。 X射线晶体学揭示了磷和各向异性HFC常数的平面结构，是从单晶的EPR光谱的角度依赖性获得的。合成了几种携带各种芳基的携带各种芳基类的三级膦，例如2,6-二烷基苯基，2,6-二苯基和2-烷基-6-甲苯基基团，合成且详细的结构，动态的立体化学，尤其是在磷酸和相互作用的磷酸盐和相互作用的反转障碍物的反转障碍物中的三分之一饲养的鸟类相互群体的繁殖物。原子。还研究了拥挤的三磷酸部分与其他功能部位之间的分子内相互作用。合成了几种携带donar或受体在4位的磷的三翼磷酶合成，并研究了对电子光谱的取代基作用。发现电子撤回组（例如甲基基团）会导致最长的吸收波长的红移，从而使红色磷橙色。通过铃木耦合和氧化还原特性与分子内电荷转移之间的关系合成了拥挤的三轮磷酸。（4-BROMO-2,6-二甲基苯基苯基）BIS（2,4,6-三环己基苯基）磷酸开发为拥挤的三级磷酸的关键合成中间体，可以将其氧化为可分离的阳离子自由基以及具有功能性位点。合成了携带两个由双苯基，偶氮和硝化连接连接的两个拥挤的三磷酸部分的双膦。