烯基取代环戊二烯基钌配合物的合成及晶体结构  

The Synthesis and Crystal Structure of Alkenyl-Substituted Cyclopentadienyl Ruthenium Complexes

作　　者：金军挺[1] 黄吉玲[1] 钱廷龙 

机构地区：[1]华东理工大学金属有机化学研究室,上海200237

出　　处：《化学学报》1999年第9期1043-1046,共4页Acta Chimica Sinica

基　　金：国家自然科学基金(29572044);南京大学配位化学国家重点实验室资助项目

摘　　要：金属氢化物的研究具有重要的理论及应用价值,它们的合成及表征揭示了氢分子在与过渡金属作用成键时,它可以作为电子给体,把σ成键轨道电子给予金属的d空轨道,而金属d轨道上的电子则反馈到H_2分子的σ^(?)反键轨道上.氢分子从分子氢配合物中的流失和它的取代反应是这类金属配合物的最普遍的性质.由分子氢的流失而产生的配位不饱和往往是很多其它作用的先决条件.各类分子氢金属配合物中氢配体的稳定性相差很大.例如Kubas合成的钨配合物W(CO)_3(PR_3)_2(H_2)中氢分子配体很容易丧失或被取代,它的结晶作用要在氢气下进行,而且还要使用配位能力较弱的烷烃或芳香族溶剂.Two alkenyl-substituted cyclopentadienyl ruthenium complexes(1,2) were synthesized. The diallylcyclopentadiene was obtained by a one-pot reaction of sodium cyclopentadienide and allyl chloride. The complex(2) with this ligand is chiral and characterized by X-ray analysis. It belongs to the triclinic space group P1 ( #2) with a = 1.1257(6) nm, b = 1. 8525(7)nm, c = 1.0134(4)nm, α =90. 89 (3)°,β= 102.77(4)°, γ=106.93(3)°. V= 1.964(1)nm3, Z = 2, Dcalc= 1.363g·cm-3, F(000) = 832. 00. The X-ray structure of complex (2) reveals that geometry around the ruthenium can be considered as distorted tetrahedral. The distance of Ru-C, Ru-P and Ru-Cl is greatly different from that in CpRu (PPh3 )2Cl. It can be concluded that the introduction of diallyl group into the cyclopentadienyl ligand results in the redistribution of electron around the ruthenium. The donation from diallyl group to cyclopentadienyl ligand weakens the back-donation from ruthenium to cyclopentadienyl ligand. Hence, the electron is transferred to PPh3, Cl ligands.

关 键 词：取代 环戊二烯 钌 配合物 手性 晶体 烯基取代 

分 类 号：O614.821[理学—无机化学]