高等学校化学学报

高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (12): 1967.

• 研究论文 • 上一篇    下一篇

苹果酸钼外消旋体的合成、光谱性质和结构表征

颜文斌1, 周朝晖2, 章慧2, 万惠霖2, 蔡启瑞2   

  1. 1. 吉首大学化学系, 吉首 416000;
    2. 厦门大学化学系, 厦门 361005
  • 收稿日期:2000-11-28 出版日期:2001-12-24 发布日期:2001-12-24
  • 通讯作者: 周朝晖(1964年出生),男,教授,从事配位催化研究.E-mail:zhzhou@xmu.edu.cn E-mail:zhzhou@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29933040);高等学校骨干教师资助计划;博士学科点基金资助

Synthesis and Spectroscopic and Structural Characterization of Racemic Ammonium Dimeric(malato)dioxomolybdenum

YAN WenBin ZHOU ZhaoHui1, ZHANG Hui2, WAN HuiLin2, Cai QiRui2   

  1. 1. Department of Chemistry, Jishou University, Jishou 416000, China;
    2. Department of Chemistry, Xiamen University, Xiamen 361005, China
  • Received:2000-11-28 Online:2001-12-24 Published:2001-12-24

PDF (PC)

被引次数

5

摘要： 钼酸铵和外消旋苹果酸溶液反应得到外消旋苹果酸钼(Ⅵ)配合物,(NH4)4[Mo∧O2(S,S-Hmal)2]·[MoΔO2(R,R-Hmal)2],对该配合物进行了元素分析、电导测定、旋光和红外光谱表征,并测定了晶体结构.该化合物晶体属单斜晶系,P21/a空间群,晶胞参数:a=0.8061(2)nm,b=1.3286(2)nm,c=1.3232(2)nm,β=91.80(2)°,V=1.4164(9)nm3,Z=2,Dc=2.008g·cm-3,F(000)=864,μ=9.70cm-1,一致性因子R=0.051,Rw=0.058.在该单核配合物阴离子中,钼上的两个苹果酸配体具有相同手性,它以α-烷氧基和α-羧基双齿配位形成畸变的八面体构型,而另一个β-羧酸则保持自由状态.

关键词: 苹果酸, 苹果酸盐, 钼(Ⅵ)配合物, 固氮酶, 晶体结构

Abstract: The complex (NH4)4[Mo∧O2(S,SHmal)2]·[MoΔO2(R,RHmal)2] was prepared from the reaction of ammonium molybdate and R,Smalic acid at pH=2——3. It was characterized by elementary analysis, conductivity measurement, optical rotation, IRand Xray diffraction. The complex crystallizes in monoclinic space group P21/a with unit cell parameters: a=0.8061(2) nm, b=1.3286(2) nm, c=1.3232(2) nm, β=91.82(2)°, V=1.4164(9) nm3, Z=2, Dc=2.008 g·cm-3, F(000)=864, μ=9.700 cm-1 for 1902 reflections with I≥3σ(I). The molybdenum atom is coordinated by two bidentate homochiral malic acid in distorted octahedron, while the βcarboxyl groups remain uncomplexed. The crystal contains two isolated monomeric malatomolybdates(Ⅵ) anions in the configurations of ∧S,S and ΔR,R. The two enantiomeric anions result in the formation of racemic compound. There is no evidence for the other diastereoisomers like (NH4)2[Mo∧O2(R,SHmal)2], (NH4)2[MoΔO2(R,SHmal)2], (NH4)2[Mo∧O2(R,RHmal)2] and (NH4)2[MoΔO2(S,SHmal)2] in this experiment.

Key words: Malic acid, Malate, Oxomolybdenum(Ⅵ) complex, Nitrogenase, Crystal structure

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