一价铜卤化物的设计合成与晶态结构研究

Design synthesis and crystalline structure of copper(I) halide complexes

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1个三核铜(I)溴化物[{Cu2(μ-dppe)(μ-Br)2}(μ-dppe)2CuBr](1)和1个双核铜(I)碘化物[{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2个Br原子和2个P原子连接构成1个变型四面体,而Cu3原子采取三配位模式,与1个Br和2个P原子相连接形成1个平面三角形,Cu1、Cu2和Cu3这3个铜原子又共同构成了1个近似等腰的平面三角形;配合物2为双核铜配合物,3个dppb配体表现出2种配位方式:2个以二齿螯合方式分别与1个Cu原子连接,1个以桥联方式与2个相同的{Cu(dppb)I}砌块相连接.

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）E}（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 Cul and Cu2 atoms adopt a common four-coordinate mode. Each connects with two bromide and two phosphorus atoms, respectively, forming a distorted tetrahedral configuration. The Cu3 atom is trigonally coordinated via two phosphorus and one bromide atoms by generating a plane triangle. These three copper（I） atoms （Cul, 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. However, the third one acts as a bridge assembling two same {Cu （dppb）I} moieties into a copper（I） dimer.