乙酸钼(II)

化合物

乙酸钼(II)是一种配位化合物,化学式为Mo2(O2CCH3)4。它是黄色抗磁性的固体,对空气稳定,微溶于有机溶剂,分子中存在Mo-Mo四重键[1]

乙酸钼(II)
别名 四乙酸二钼
二乙酸钼二聚体
识别
CAS号 14221-06-8  checkY
PubChem 84269
ChemSpider 76023
SMILES
 
  • [Mo-2]1234#[Mo-2]([o+]c(C)o1)([o+]c(C)o2)(oc(C)[o+]3)oc(C)[o+]4
性质
化学式 C8H12Mo2O8
摩尔质量 428.1010 g/mol g·mol⁻¹
外观 黄色固体
沸点 分解
溶解性 不溶
危险性
警示术语 R:20/21/22, 36/37/38
安全术语 S:7/9, 22, 24/25, 29/35, 42, 43, 64
相关物质
相关化学品 乙酸铜
乙酸亚铬
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

结构

乙酸钼(II)具有中国灯笼结构,与乙酸亚铑乙酸铜乙酸亚铬这类二聚乙酸盐同构,[2]Mo2(O2CCH3)4晶体属三斜晶系,P1空间群,[3]分子中的每个Mo中心有四个d层價電子,两个Mo的八个d电子形成一个σ鍵、两个π键和一个δ键,形成σ2π4δ2电子排布。四个乙酸根桥联两个金属中心。Mo-O的键长为2.119 Å,Mo-Mo的键长为2.0934 Å。[4]

制备

乙酸钼(II)可由六羰基钼乙酸反应得到,反应中羰基配體被乙酸根取代,放出一氧化碳,钼从零价氧化至正二价。[5][6]

2 Mo(CO)6 + 4 HO2CCH3 → Mo2(O2CCH3)4 + 12 CO + 2 H2

反应会产生三核簇作为副产物。[7]

六羰基钼和乙酸的反应最初由班尼斯特于1960年使用,当时金属-金属四重键未被发现,作者认为制得的Mo(O2CCH3)2具有四面体构型。[8][9]后来,梅森对其表征,改变了这一观点。[10]

应用

Mo2(O2CCH3)4可用于制备其它含四重键的钼化合物,[1]反应中,乙酸根配体可以被其它配体取代,如[Mo2Cl8]4−和Mo2Cl4[P(C4H9)3]4[1][11][12]

参考文献

  1. ^ 1.0 1.1 1.2 Girolami, G. S.; Rauchfuss, T. B. and Angelici, R. J., "Synthesis and Technique in Inorganic Chemistry third edition", University Science Books: Mill Valley, CA, 1999, ISBN 0-935702-48-2
  2. ^ Cotton, F. Albert; Hillard, Elizabeth A.; Murillo, Carlos A.; Zhou, Hong-Cai. After 155 Years, A Crystalline Chromium Carboxylate with a Supershort Cr−Cr Bond. Journal of the American Chemical Society. 2000, 122 (2): 416–417. ISSN 0002-7863. doi:10.1021/ja993755i. 
  3. ^ Cotton, F. A.; Mester, Z. C.; Webb, T. R. Dimolybdenum tetraacetate. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 1974, 30 (11): 2768–2770. ISSN 0567-7408. doi:10.1107/S0567740874008053. 
  4. ^ Blaudeau, Jean-Philippe; Pitzer, Russell M. Ab Initio Studies of Ligand Effects on the Metal-Metal Bond in Dimolybdenum Complexes. The Journal of Physical Chemistry. 1994, 98 (17): 4575–4579. ISSN 0022-3654. doi:10.1021/j100068a016. 
  5. ^ Brignole, Alicia B.; Cotton, F. A.; Dori, Z.; Dori, Z.; Dori, Z.; Wilkinson, G. Rhenium and Molybdenum Compounds Containing Quadruple Bonds: 81–89. 2007. ISSN 1934-4716. doi:10.1002/9780470132449.ch15. 
  6. ^ Pence, Laura E.; Weisgerber, Amy M.; Maounis, Florence A. Synthesis of Molybdenum-Molybdenum Quadruple Bonds: A Multistep Advanced Synthesis Laboratory Experiment. Journal of Chemical Education. 1999, 76 (3): 404. ISSN 0021-9584. doi:10.1021/ed076p404. 
  7. ^ Bino, Avi; Cotton, F. Albert; Dori, Zvi. A new aqueous chemistry of organometallic, trinuclear cluster compounds of molybdenum. Journal of the American Chemical Society. 1981, 103 (1): 243–244. ISSN 0002-7863. doi:10.1021/ja00391a068. 
  8. ^ Bannister, E.; Wikinson, G. “Molybdenum(II) carboxylates” Chem. Ind. 1960, 319.
  9. ^ Stephenson, T. A.; Bannister, E.; Wilkinson, G. 487. Molybdenum(II) carboxylates. Journal of the Chemical Society (Resumed). 1964: 2538. ISSN 0368-1769. doi:10.1039/jr9640002538. 
  10. ^ Lawton, D.; Mason, R. The Molecular Structure of Molybdenum(II) Acetate. Journal of the American Chemical Society. 1965, 87 (4): 921–922. ISSN 0002-7863. doi:10.1021/ja01082a046. 
  11. ^ Tsai, Yi-Chou; Chen, Hong-Zhang; Chang, Chie-Chieh; Yu, Jen-Shiang K.; Lee, Gene-Hsiang; Wang, Yu; Kuo, Ting-Shen. Journey from Mo−Mo Quadruple Bonds to Quintuple Bonds. Journal of the American Chemical Society. 2009, 131 (35): 12534–12535. ISSN 0002-7863. doi:10.1021/ja905035f. 
  12. ^ Handa, Makoto; Mikuriya, Masahiro; Kotera, Takanori; Yamada, Kori; Nakao, Tadahiro; Matsumoto, Hiroki; Kasuga, Kuninobu. Linear Chain Compounds of Molybdenum(II) Acetate Linked by Pyrazine, 4,4′-Bipyridine, and 1,4-Diazabicyclo[2.2.2]octane. Bulletin of the Chemical Society of Japan. 1995, 68 (9): 2567–2572. ISSN 0009-2673. doi:10.1246/bcsj.68.2567.