zh 乙酸钼(II)

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
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（水）	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。

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]

结构

乙酸钼(II)具有中国灯笼结构，与乙酸亚铑、乙酸铜和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)可由六羰基钼和乙酸反应得到，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

^ ^1.0 ^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.

[girolami-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.

[blaudeau-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.

[brignole-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.

[pence-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.

[bannister-8] Bannister, E.; Wikinson, G. “Molybdenum(II) carboxylates” Chem. Ind. 1960, 319.

[stephenson-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.

[handa-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.

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乙酸钼(II)

结构

制备

应用

参考文献

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