二氯二氧化钼

二氯二氧化钼
英文名	Molybdenum dichloride dioxide; Molybdyl chloride
识别
CAS号	13637-68-8
PubChem	139520
SMILES	O=[Mo](Cl)(Cl)=O;
性质
化学式	Cl2MoO2
摩尔质量	198.84 g·mol−1
外观	浅黄色固体
熔点	298 °C（571 K）（文献a）; 159 °C（432 K）（升华，文献b）
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二氯二氧化钼是一种无机化合物，化学式为MoO₂Cl₂。它是浅黄色可溶于水的潮解性固体，可用于制备其它钼化合物。它的加合物MoO₂Cl₂(ether)₂可溶于有机溶剂。二氯二氧化钼可用作一些氧化反应的催化剂。^[3]

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二氯二氧化钼可由三氧化钼和浓盐酸反应得到：^[4]

MoO₃ + 2 HCl → MoO₂Cl₂ + H₂O

MoO₂Cl₂也能以MoOCl₄为原料制备：^[5]

MoOCl₄ + O(Si(CH₃)₃)₂ → MoO₂Cl₂ + 2 ClSi(CH₃)₃

二氧化钼于500~700 °C和氯气反应^[6]，或者五氯化钼在空气中加热也能得到产物：

MoO₂ + Cl₂ → MoO₂Cl₂

2 MoCl₅ + 2 O₂ → 2 MoO₂Cl₂ + 3 Cl₂

MoO₃和CCl₄在713~753 K反应，可以得到二氯二氧化钼，气态产物包括二氧化碳、氯气和光气。^[7]

化学性质

MoO₂Cl₂可以形成一系列的加合物，例如MoO₂Cl₂(THF)₂。它和大分子苯胺反应，生成二亚胺配合物MoCl₂(NAr)₂(L)，这种配合物是Schrock型卡宾Mo(OR)₂(NAr)(CH-t-Bu)的前驱体。^[6]

MoO₂Cl₂可以和干燥的氟化氢或三氧化硫磺酰氯溶液反应：

MoO₂Cl₂ + 2 HF → MoO₂F₂ + 2 HCl

MoO₂Cl₂ + 3 SO₃ → MoO(SO₄)₂ + SO₂Cl₂

参考文献

[1]
Eliseev, S. S.; Malysheva, L. E.; Vozhdaeva, E. E. Methods for synthesis and thermal properties of molybdenum dioxychloride (MoO₂Cl)（俄文）. Zhurnal Neorganicheskoi Khimii, 1985. 30 (2): 296-300. ISSN: 0044-457X.
[2]
Saeki, Yuzo; Matsuzaki, Ryoko. Chemistry of molybdenum chlorides. V. Thermochemical properties of molybdenum dioxydichloride（日语）. Denki Kagaku, 1966. 34 (7): 504-505. ISSN: 0366-9440.
[3]
Marta Castiñeira Reis, Marta Marín-Luna, Carlos Silva López, Olalla Nieto Faza. [MoO 2 ] 2+ -Mediated Oxygen Atom Transfer via an Unusual Lewis Acid Mechanism. Inorganic Chemistry. 2017-09-05, 56 (17): 10570–10575 [2019-03-28]. ISSN 0020-1669. doi:10.1021/acs.inorgchem.7b01529 （英语）.
[4]
Francisco J. Arnaiz. Dichlorodioxobis(Dimethylsulphoxide) Molybdenum(VI). Inorganic Syntheses. 1997, 31: 246-7. doi:10.1002/9780470132623.ch39.
[5]
Gibson, V. C.; Kee, T. P.; Shaw, A. New, improved synthesis of the group 6 oxyhalides, W(O)Cl₄, W(O)₂Cl₂ and Mo(O)₂Cl₂. Polyhedron. 1988, 7 (7): 579–80. doi:10.1016/S0277-5387(00)86336-6.
[6]
Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. Synthesis of molybdenum imido alkylidene complexes and some Reactions Involving Acyclic Olefins. Journal of the American Chemical Society. 1990, 112: 3875–3886. doi:10.1021/ja00166a023.
[7]
Del Carmen Ruiz, Maria; Rivarola, Juan B.; Quiroga, Oscar D. Chlorination of molybdenum trioxide with carbon tetrachloride. Latin American Applied Research, 1990. 20 (2): 107-111. ISSN: 0327-0793.

拓展阅读

Korshunov, B. G.; Nirsha, B. M. Reaction of molybdenum dioxydichloride with chloride compounds of Groups IV and V elements（俄文）. Zhurnal Neorganicheskoi Khimii, 1969. 14 (7): 1971-1972. ISSN: 0044-457X.

[1] [1]
Eliseev, S. S.; Malysheva, L. E.; Vozhdaeva, E. E. Methods for synthesis and thermal properties of molybdenum dioxychloride (MoO₂Cl)（俄文）. Zhurnal Neorganicheskoi Khimii, 1985. 30 (2): 296-300. ISSN: 0044-457X.

[2] [2]
Saeki, Yuzo; Matsuzaki, Ryoko. Chemistry of molybdenum chlorides. V. Thermochemical properties of molybdenum dioxydichloride（日语）. Denki Kagaku, 1966. 34 (7): 504-505. ISSN: 0366-9440.

[3] [3]
Marta Castiñeira Reis, Marta Marín-Luna, Carlos Silva López, Olalla Nieto Faza. [MoO 2 ] 2+ -Mediated Oxygen Atom Transfer via an Unusual Lewis Acid Mechanism. Inorganic Chemistry. 2017-09-05, 56 (17): 10570–10575 [2019-03-28]. ISSN 0020-1669. doi:10.1021/acs.inorgchem.7b01529 （英语）.

[4] [4]
Francisco J. Arnaiz. Dichlorodioxobis(Dimethylsulphoxide) Molybdenum(VI). Inorganic Syntheses. 1997, 31: 246-7. doi:10.1002/9780470132623.ch39.

[5] [5]
Gibson, V. C.; Kee, T. P.; Shaw, A. New, improved synthesis of the group 6 oxyhalides, W(O)Cl₄, W(O)₂Cl₂ and Mo(O)₂Cl₂. Polyhedron. 1988, 7 (7): 579–80. doi:10.1016/S0277-5387(00)86336-6.

[RRS-6] [6]
Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. Synthesis of molybdenum imido alkylidene complexes and some Reactions Involving Acyclic Olefins. Journal of the American Chemical Society. 1990, 112: 3875–3886. doi:10.1021/ja00166a023.

[7] [7]
Del Carmen Ruiz, Maria; Rivarola, Juan B.; Quiroga, Oscar D. Chlorination of molybdenum trioxide with carbon tetrachloride. Latin American Applied Research, 1990. 20 (2): 107-111. ISSN: 0327-0793.

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