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二茂锇

二茂锇
IUPAC名
osmocene, bis(η5-cyclopentadienyl)osmium
别名 di(cyclopentadienyl)osmium
识别
CAS号 1273-81-0  checkY
PubChem 6432038
ChemSpider 71493
SMILES
 
  • [cH-]1cccc1.[cH-]1cccc1.[Os+2]
InChI
 
  • 1/2C5H5.Os/c2*1-2-4-5-3-1;/h2*1-5H;/q2*-1;+2
InChIKey RMYKEUKAFJLONI-UHFFFAOYAC
性质
化学式 C10H10Os
摩尔质量 320.42 g·mol−1
外观 白色固体
熔点 234℃
沸点 298℃
结构
晶体结构 orthorhombic
空间群 Pnma, No. 62
相关物质
相关化学品 二茂铁二茂钌
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

二茂锇有机锇化合物英语organoosmium compound,呈白色固体,是茂金属,化学式Os(C5H5)2

制备

二茂锇可作为商品购买,亦能以四氧化锇氢溴酸反应,然后同环戊二烯反应来制备。[1]

二茂锇由恩斯特·奥托·菲舍尔和海因里希·格莱姆伯特首次制备。他们的制备方法是使四氯化锇和过量的环戊二烯钠乙二醇二甲醚中反应,其中二氯化锇可能是原位形成的中间体。环戊二烯基溴化镁英语Cyclopentadienyl magnesium bromide可与四氯化锇反应,生成二茂锇,但产率较低。[2]

性质

二茂锇是白色固体。分子结构的特征是锇离子夹在两个茂基之间。它与较轻的同系物二茂钌同构,均以重叠的构象结晶。这与二茂铁相反,后者的环错位。[1]

与二茂铁和二茂钌相比,二茂锇对亲电子芳香族取代反应的活性较低,但它最容易与路易斯酸反应,形成加合物[3]

二茂锇阳离子[Os(C5H5)2]+会二聚,形成含有Os-Os键的二聚体。[4]相较来说,十甲基二茂锇阳离子[Os(C5(CH3)5)2]+单体稳定。[5]

用处

2009年,霍斯特·孔克里和阿恩德·弗格勒的报告表明以二茂锇为催化剂可能实现光催化水分解[6]

参考资料

  1. ^ 1.0 1.1 Bobyens, J. C. A.; Levendis, D. C.; Bruce, Michael I.; Williams, Michael L. Crystal structure of osmocene, Os(η-C5H5)2. Journal of Crystallographic and Spectroscopic Research. 1986, 16 (4): 519. doi:10.1007/BF01161040. 
  2. ^ Fischer, Ernst Otto; Grumbert, Heinrich. Über Aromatenkomplexe von Metallen, XXIX. Di-cyclopentadienyl-osmium. Chem. Ber. 1959, 92 (9): 2302–2309. doi:10.1002/cber.19590920948. 
  3. ^ Kur, Sally A.; Rheingold, Arnold L.; Winter, Charles H. Synthesis, Characterization, and Halogenation of Decakis( acetoxymercurio)osmoene. Crystal and Molecular Structure of Decachloroosmocene. Inorg. Chem.: 414-416. doi:10.1021/ic00105a067. 
  4. ^ Droege, Michael W.; Harman, W. Dean; Taube, Henry. Higher Oxidation State Chemistry of Osmocene: Dimeric Nature of the Osmocenium Ion. Inorg. Chem.: 1309–1315. doi:10.1021/ic00255a023. 
  5. ^ Astruc, Didier. Metallocenes and Sandwich Complexes. Organometallic Chemistry and Catalysis. Springer-Verlag. 2007: 263. ISBN 978-3-540-46128-9. doi:10.1007/978-3-540-46129-6_13. 
  6. ^ Kunkely, Horst; Vogler, Arnd. Water Splitting by Light with Osmocene as Photocatalyst. Angew. Chem. Int. Ed. 2009, 48 (9): 1685–1687. doi:10.1002/anie.200804712. 
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二茂锇
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