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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.

开发了性能优良的密集三芳基膦。合成了最密集的三芳基膦之一的三(2，4，6-三环己基苯基)膦，并用亚硝酸盐氧化制备了相应的阳离子自由基，并首次以紫色晶体的形式分离出来作为三芳基膦的阳离子自由基。X射线结晶学研究表明，磷的平面结构和各向异性的HFC常数是由单晶EPR谱的角度关系得到的。合成了含有2，6-二烷基苯基、2，6-二芳基苯基和2-烷基-6-芳基苯基等不同芳基的稠密三芳基膦类化合物，详细的结构、动态立体化学，特别是膦的反转势垒和由磷原子上的三个芳环组成的螺旋桨螺旋度引起的异构体的相互转化。此外，我们还研究了拥挤的三芳基膦部分与其他功能位之间的分子内相互作用。合成了几种三芳基膦类化合物，并研究了取代基对电子光谱的影响。甲酰基等吸电子基团引起最长吸收波长的红移，使橙色的膦变成红色的膦。采用Suzuki偶联法合成了含对苯二酚的密集三芳基膦化合物，系统地阐明了氧化还原性质与分子内电荷转移的关系。(4-Bromo-2，6-dicyclohexylphenyl)bis(2，4，6-tricyclohexylphenyl)phosphine是合成密集三芳基膦的关键合成中间体，它可以被氧化成可分离的阳离子自由基，并且具有功能位点。合成了通过联苯、偶氮和氮氧键连接的两个密集的三芳基膦基团的双膦配体。