一种新颖钒.钨异金属八核簇合物[VW~3~4(O~2CEt)~8]~2Na~2的合成与结构

本文报道了一种钒.钨异金属八核簇合物VW~3~4(O~2CEt)~8]~2Na~2(1)在恒温液相条件下的合成与结构研究,晶体属三斜晶系,P1空间群,a=1.2973(4),b=1.4063(3),c=1.2396(5)nm,α=1.09.92(2),β=117.32(2),γ=90.53(2)°,V=1.8513nm^3,D~c=2.29g/cm^3,Z=1对5499个可观测反射点I>3σ(I)] 最终一致性因子为R=0.030.单晶结构分析表明,簇阴离子中两个W~3O~4]^4^+单元通过两个"桥"金属V原子联接成一个奇特的环状结构,W-W平均键长为0.25328(6)nm,W...V间平均距离为0.3654nm,簇阴离子通过Na^+联成一个一维长链.Na 原子具有少见的五配位,Na-O距离仅为0.2314nm,Na-O间教情的相互作用以及无限长链的晶体结构很好地解释乐簇合物1的稳定性和不溶性.

The synthesis and structure of a novel octanuclear mixed-metal cluster [VW~3~4(O~2CEt)~8]~2Na~2

The insoluble octanuclear mixed-metal cluster Na2VW3O4(O2CEt)8]2 (1) was prepared by the redox reaction of W(CO)6 with NaVO3 in propionic anhydride. The crystal is triclinic of space group P1 with a 1.2973(4), b 1.4063(3), c 1.2396(5) nm, a 109.92(2), b 117.33(2), g 90.53(2)? dc = 2.29 g/cm3, Z = 1, final R = 0.030 for 5499 observed reflections I > 3s(I)]. The structure of the compound consists of an interesting centrosym. anion, where two W3O4]4+ units are connected by two V atoms to complete a circular specie. The average W-W bond length is 0.25328(6) nm and the average distance between V and W atoms is 0.3654 nm. The anions are connected by Na+ to form a 1-dimensional infinite chain structure. Each Na atom is coordinated to five O atoms with average Na-O distance of 0.2314 nm. The short Na-O distance and chain structure are responsible for the insoly. of the cluster 1.