乙酸鉬(II)

乙酸鉬(II)
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	[Mo-2]1234#[Mo-2]([o+]c(C)o1)([o+]c(C)o2)(oc(C)[o+]3)oc(C)[o+]4;
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。

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]

結構[編輯]

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[編輯]

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[編輯]

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[編輯]

^ ^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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