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文章编号： 一价铜卤化物的设计合成与晶态结构研究( 谭秀珍，陈景林，曹兴付，陈琇琇，张 凤，温和瑞，廖金生 （江西理工大学冶金与化学工程学院江西 赣州 341000） 摘 要：文中以1,2-双(二苯基膦)乙烷(dppe)、1,4-双(二苯基膦)丁烷(dppb)和卤化亚铜作为初始原料，合成得到一三核铜(I)化物[{Cu2(μ-dppe)(μ-Br)2}(μ-dppe)2CuBr] (1) 和一双核铜(I)化物[{Cu(dppb)I}2(μ-dppb)] (2). X-射线单晶衍射表明：配合物1为三核铜配合物，Cu1和Cu2两原子采用常见的四配位方式，分别与两个Br和两个P原子连接构成一个变型四面体，而Cu3原子采取三配位模式，与一个Br和两个P原子相连接形成一个平面三角形， Cu1、Cu2和Cu3这三个铜原子又共同构成一个近似等腰的平面三角形；配合物2为核铜配合物，三个dppb配体表现出两种配位方式：两个以二齿螯合方式分别与一个Cu原子连接，一个以桥联方式与两个{Cu(dppb)I}砌块相连接. 关键词：一价铜卤化物；双膦配体；晶体结构；三核配合物；双核配合物 中图分类号：TF811 文献标识码：A Designed synthesis and crystalline structure of copper(I) halide complexes TAN Xiu-zhen, CHEN Jing-lin, CAO Xing-fu, CHEN Xiu-xiu, ZHANG Feng, WEN He-rui, LIAO Jin-sheng (Faculty of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China) Abstract: Utilizing 1,2-bis(diphenylphosphino)ethane (dppe), 1,4-bis(diphenylphosphino)butane (dppb), and cuprous halide as the starting materials, a trinuclear copper(I) bromide complex [{Cu2(μ-dppe)(μ-Br)2}(μ-dppe)2CuBr] (1) and a binuclear copper(I) iodide complex [{Cu(dppb)I}2(μ-dppb)] (2) were synthesized and structurally characterized. As revealed by single-crystal X-ray diffraction, compound 1 is a trinuclear copper(I) complex, in which the Cu1 and Cu2 atoms adopt a common four-coordinate mode, and each connects with two bromide and two phosphorus atoms, respectively, forming a distorted tetrahedral configuration, while the Cu3 atom is trigonally coordinated via two phosphorus and one bromide atoms and then generates a plane triangle, furthermore, these three copper(I) atoms (Cu1, Cu2, Cu3) give a nearly isosceles triangle together. Compound 2 is a binuclear Cu(I) complex, in which these three dppb ligands offer two kinds of coordination fashions: two of them are chelating, one for each copper atom, whereas the third one acts as a bridge assembling two same {Cu(dppb)I} moieties into a copper(I) dimer. Key words: copper(I) halide complex; diphosphine; cryst