高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (8): 1470.

• 研究论文 • 上一篇    下一篇

四核钴羰基簇合物的合成和晶体结构

吴秉芳1, 张富强1, 刘树堂1, 胡襄1, 金祥林2   

  1. 1. 内蒙古大学化学化工学院, 呼和浩特 010021;
    2. 北京大学化学和分子工程学院, 北京 100871
  • 收稿日期:2001-04-18 出版日期:2002-08-24 发布日期:2002-08-24
  • 作者简介:吴秉芳(1943年出生),女,教授,从事过渡金属原子簇化学研究.
  • 基金资助:

    国家自然科学基金(批准号:29861001);内蒙古教育厅科学基金(ZD01071)资助

Synthesis and Crystal Structure of Tetranuclear Cobalt Carbonyl Clusters

WU Bing-Fang1, ZHANG Fu-Qiang1, LIU Shu-Tang1, HU Xiang1, JIN Xiang-Lin2   

  1. 1. College of Chemistry and Chemical Engineering, Neimongol University, Hohhot 010021, China;
    2. College of Chemistry and Molecular Engineering, Beijing University, Beijing, 100871, China
  • Received:2001-04-18 Online:2002-08-24 Published:2002-08-24

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被引次数

7

摘要： 用Co2(CO)8与有机杂环二硫代次膦酸盐SP(C6H4OR)(S)N(C6H5)NC(Me)(R=Me,Et)反应,得到两类4个含S,P桥基配体的四核钴羰基簇合物Co4(CO)10(μ4-S)[μ4-P(C6H4OR)](1:R=Me;3:R=Et)和Co4(CO)10(μ3-S)[μ2-P(C6H4OR)N(C6H5)NC(Me)](2:R=Me,4:R=Et).在反应中,前配体中的PS键以及C—S,P—S,P—N键劈开,产生的分子片与金属钴原子配位,组建成新的羰基钴簇.对这4个簇合物进行了元素分析,IR,1HNMR和MS谱学表征,并测定了簇合物4的晶体结构,该晶体属单斜晶系,P21/c空间群,晶胞参数a=1.9065(4)nm,b=1.0081(2)nm,c=1.6663(3)nm,β=97.36(3)°,V=3.1704(11)nm3,Z=4,Dc=1.743g/cm3.Co1Co3Co4呈三角形分布,其中Co—Co平均键长为0.251nm,而Co2在该三角平面的一侧,Co2—Co3键为0.269nm.该簇合物分子骨架为三角钉型结构,每个Co原子的立体几何均为变形八面体,但配位环境各不相同.

关键词: 钴羰基簇合物, 劈开组合合成法, 晶体结构

Abstract: The reactions of Co2(CO)8 with organic cyclic dithiophosphinate SP(S)(C6H4OR)N(C6H5)NC(Me)(R=Me, Et) gave four tetranuclear cobalt carbonyl clusters containing capping S, Pbridging ligand in Co 4(CO)10 (μ4-S) (μ4-PC6H4OR)(1: R=Me, 3: R=Et) and P⌒Cbridging and face bridging Sligand in Co4 (CO)10 (μ3-S)[μ2-P(C6H4OR)N(Ph)NCMe](2:R=Me, 4:R=Et). During the reactions, the two ligand precursors have cleaved in its PSand/or C-S, P-S, P-Nbonds respectively to give the fragments as the ligand as listed above that coordinated to Co atoms to form the new cluster molecules. These clusters have characterized by elementary analysis, IR, 1H NMRand MSspectroscopy. The crystal structure of cluster 4 has been determined by X-ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The cell parameters are as follows: a=1.9065(4) nm, b=1.0081(2) nm, c=1.6663(3) nm, β=97.36(3)°, V=3.1704(11) nm3, Dc=1.743 g/cm3, Z=4. The Co-Co average bond length is 0.251 nm in the triangular plane of Co1Co3Co4, the Co2 is linked on the plane to form a spike. The tetracobalt framework is "spiked triangular". The stereogeometry of each Co assumes a distorted octahedron with different coordination environments.

Key words: Cobalt carbonyl cluster, Cleavage and combination synthesis method, Crystal structure

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