含M-C键的三齿配位钯和铂化合物的合成与应用研究

项目名称： 含M-C键的三齿配位钯和铂化合物的合成与应用研究

项目编号： No.20872133

项目类型： 面上项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 宋毛平

作者单位： 郑州大学

项目金额： 40万元

中文摘要： 钯催化的碳-碳键生成反应在药物、天然产物及功能性材料等分子的合成中有着重要应用，含Pd-C键的三齿配位钳形钯化合物是其中一类有效的催化剂；而同类型的铂化合物是潜在的有机电致磷光材料。本项目合成了多种新型的含M-C键的三齿配位钳形钯和铂化合物，包括：手性的(咪唑啉)(二烃基膦氧)、(咪唑啉)(氨基膦)、(咪唑啉)(亚膦酰胺)PCN型和双(亚膦酰胺)PCP型、非手性的(吡唑)(二烃基膦氧)PCN型、2-胺甲基-6-苯基吡啶CNN和相关的NCN型钯化合物(其中含膦的钯化合物通过本课题组发展的"一锅煮"膦化/钯化反应合成)；铂化合物有双(咪唑啉)NCN铂炔化合物、双(苯并咪唑)NCN铂卤和铂炔化合物。对所有的新化合物进行了结构表征。非手性的钯化合物能有效地催化Suzuki、Sonogashira、醛的烯丙基化以及醛、胺和烯丙基锡的三组分反应等；手性的钯化合物被用于催化不对称Suzuki反应(最高32% ee值)、醛或N-磺酰亚胺与烯丙基锡的不对称加成反应(最高69% ee值)以及二芳基膦烷与a,β#19981;饱和酮的不对称加成反应(最高94% ee值)等。此外，考察了铂化合物的光致发光性能。

中文关键词： M-C键；三齿配位；钳形钯和铂化合物；催化；光致发光

英文摘要： Palladium-catalyzed carbon-carbon bond-forming reactions have found important applications in the preparation of drugs, natural products as well as functional materials. Tridentate coordinated pincer palladium(II) complexes containing Pd-C bonds are efficient catalysts for some of these reactions. And the platinum(II) complexes of the same kind have been found to be potential electrophosphorescent materials. In this project, a variety of new pincer Pd and Pt complexes containing M-C bonds have been synthesized. The Pd complexes include chiral (imidazolinyl)phosphinite, (imidazolinyl)- (aminophosphine), (imidazolinyl)(phosphoramidite) PCN and bis(phosphoramidite) PCP, achiral (pyrazolyl)phosphinite PCN, 2-aminomethyl-6-phenylpyridine CNN and the related NCN type complexes. Among them, the P-donor containing complexes were conveniently prepared by the "one-pot phosphorylation/palladation" method developed by us. The Pt complexes include bis(imidazoline) NCN alkynylplatinum as well as bis(benzimidazole) NCN halo- and alkynylplatinum complexes. All the new compounds including ligand precursors and complexes have been well characterized. The obtained achiral Pd complexes were found to be effective catalysts for the Suzuki, Sonogashira, allylation of aldehydes as well as three-component allylation of aldehydes, arylamines and allyltributyltin. While the chiral ones have been used as catalysts for asymmetric Suzuki (up to 32% ee), allylation of aldehyde and sulfonimine (up to 69 ee%) as well as addition of diarylphosphines to enones (up to 94% ee).In addition, the photoluminescent properties of the obtained Pt complexes have been investigated.

英文关键词： M-C bond; tridentate coordinated; pincer palladium(II) and platinum(II) complexes; catalysis; photoluminescent