乙酸鉬(II)
化合物
乙酸鉬(II)是一種配位化合物,化學式為Mo2(O2CCH3)4。它是黃色抗磁性的固體,對空氣穩定,微溶於有機溶劑,分子中存在Mo-Mo四重鍵。[1]
乙酸鉬(II) | |||
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別名 | 四乙酸二鉬 二乙酸鉬二聚體 | ||
識別 | |||
CAS號 | 14221-06-8 | ||
PubChem | 84269 | ||
ChemSpider | 76023 | ||
SMILES |
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性質 | |||
化學式 | C8H12Mo2O8 | ||
摩爾質量 | 428.1010 g/mol g·mol⁻¹ | ||
外觀 | 黃色固體 | ||
沸點 | 分解 | ||
溶解性(水) | 不溶 | ||
危險性 | |||
警示術語 | R:20/21/22, 36/37/38 | ||
安全術語 | S:7/9, 22, 24/25, 29/35, 42, 43, 64 | ||
相關物質 | |||
相關化學品 | 乙酸銅 乙酸亞鉻 | ||
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。 |
結構
乙酸鉬(II)具有中國燈籠結構,與乙酸亞銠、乙酸銅和乙酸亞鉻這類二聚乙酸鹽同構,[2]Mo2(O2CCH3)4晶體屬三斜晶系,P1空間群,[3]分子中的每個Mo中心有四個d層價電子,兩個Mo的八個d電子形成一個σ鍵、兩個π鍵和一個δ鍵,形成σ2π4δ2電子排布。四個乙酸根橋聯兩個金屬中心。Mo-O的鍵長為2.119 Å,Mo-Mo的鍵長為2.0934 Å。[4]
製備
乙酸鉬(II)可由六羰基鉬和乙酸反應得到,反應中羰基配體被乙酸根取代,放出一氧化碳,鉬從零價氧化至正二價。[5][6]
- 2 Mo(CO)6 + 4 HO2CCH3 → Mo2(O2CCH3)4 + 12 CO + 2 H2
反應會產生三核簇作為副產物。[7]
六羰基鉬和乙酸的反應最初由班尼斯特於1960年使用,當時金屬-金屬四重鍵未被發現,作者認為製得的Mo(O2CCH3)2具有四面體構型。[8][9]後來,梅森對其表徵,改變了這一觀點。[10]
應用
Mo2(O2CCH3)4可用於製備其它含四重鍵的鉬化合物,[1]反應中,乙酸根配體可以被其它配體取代,如[Mo2Cl8]4−和Mo2Cl4[P(C4H9)3]4。[1][11][12]
參考文獻
- ^ 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
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ Bannister, E.; Wikinson, G. 「Molybdenum(II) carboxylates」 Chem. Ind. 1960, 319.
- ^ 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.
- ^ 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.
- ^ 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.
- ^ 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.