顺式/反式双齿膦单核钌化合物的合成、晶体结构和光谱研究  

Syntheses,crystal structural and spectral studies ofcis/trans-chelating diphosphines mononuclear ruthenium

作　　者：彭佩 王勇 PENG Pei;WANG Yong(Hubei Key Laboratory of Drug Synthesis and Optimization,College of Chemical Engineering and Pharmacy,Jingchu University of Technology,Jingmen 448000,Hubei,China)

机构地区：[1]荆楚理工学院化工与药学院,药物合成与优化湖北省重点实验室,湖北荆门448000

出　　处：《西北师范大学学报（自然科学版）》2023年第4期80-88,共9页Journal of Northwest Normal University(Natural Science)

基　　金：湖北省自然科学基金资助项目(2022CFB531)。

摘　　要：将RuCl_(2)(DMSO)4分别与双膦配体dppm或dppe反应制得单核钌化合物cis-Ru(dppm)2Cl_(2)(1)和trans-Ru(dppe)_(2)Cl_(2)(4)(dppm=双(二苯基膦基)甲烷,dppe=1,2-双(二苯基膦基)乙烷,DMSO=二甲亚砜),将RuCl_(2)(PPh_(3))_(3)分别与dppm或dppe配体反应获得单核钌化合物trans-Ru(dppm)2Cl_(2)(2)和cis-Ru(dppe)_(2)Cl_(2)(3).对化合物1~4分别进行了电子吸收光谱,IR,元素分析,1HNMR,13 CNMR,31 PNMR和单晶X射线衍射等分析表征.紫外-可见光谱和荧光光谱表明,化合物1~4中均存在金属到配体电荷转移(MLCT),且还对顺反异构体的光谱进行了分析.晶体结构数据和紫外-可见光谱均表明顺式构型比反式异构体具有更低的能量,是一种更稳定的结构.The compunds cis-Ru(dppm)2Cl_(2)(1)and trans-Ru(dppe)_(2)Cl_(2)(4)are synthesized by treatment of RuCl_(2)(DMSO)4 with dppm or dppe,respectively(dppm=bis(diphenylphosphino)methane,dppe=1,2-bis(diphenylphosphino)ethane,DMSO=dimethyl sulfoxide).Compounds trans-Ru(dppm)2Cl_(2)(2)and cis-Ru(dppe)_(2)Cl_(2)(3)are obtained by reaction of RuCl_(2)(PPh_(3))_(3)with dppm or dppe,separately.Compounds 1~4 are fully characterized by UV-Vis spectra,IR,elemental analysis,1HNMR,13 CNMR,31 PNMR and single crystal X-ray diffraction analysis.Both UV-Vis and fluorescence spectra indicated that there exit metal-to-ligand charge transfer(MLCT)in compounds 1~4,and the spectra of cis-trans isomerism are also compared and analyzed.Both the crystal structure data and UV-Vis spectra suggested that the cis-isomer has lower energy than the trans-isomer and is a more stable structure.

关 键 词：钌 双膦配体 晶体结构 紫外-可见光谱 

分 类 号：O621.3[理学—有机化学]