乙酸钼(II)

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。 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，Mo2(O2CCH3)4晶体属三斜晶系，P1空间群，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。 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。 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。 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。后来，梅森对其表征，改变了这一观点。 Mo2(O2CCH3)4可用于制备其它含四重键的钼化合物，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。 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.