Molybdenum dichloride dioxide

Molybdenum dichloride dioxide is the inorganic compound with the formula MoO2Cl2. It is a yellow diamagnetic solid that is used as a precursor to other molybdenum compounds. Molybdenum dichloride dioxide is one of several oxychlorides of molybdenum.

Molybdenum dichloride dioxide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.157.480
  • InChI=1S/2ClH.Mo.2O/h2*1H;;;
    Key: ASLHVQCNFUOEEN-UHFFFAOYSA-N
  • O=[Mo]=O.Cl.Cl
Properties
Cl2MoO2
Molar mass 198.85 g·mol−1
Appearance yellow or cream solid
Melting point 175 °C (347 °F; 448 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Structure

Gaseous molybdenum dichloride dioxide is a monomer,[1] but upon condensation, it polymerizes to give a coordination polymer of uncertain structure.

Preparation

The compound is most easily prepared by treatment molybdenum trioxide with concentrated hydrochloric acid:[2]

MoO3 + 2 HCl → MoO2Cl2 + H2O

MoO2Cl2 can also be prepared from MoOCl4:[3]

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

It is also prepared by chlorination of molybdenum dioxide:[4]

MoO2 + Cl2 → MoO2Cl2

It is also prepared by chlorination of molybdenum trixoide:[5]

MoO3 + Cl2 → MoO2Cl2

Reactions

Many bisadducts are known of the type MoO2Cl2(ether)2. These octahedral molecular complexes are soluble in organic solvents.

With bulky anilines, it converts to the diimido complex MoCl2(NAr)2(dimethoxyethane). This complex is the precursor to the Schrock carbenes of the type Mo(OR)2(NAr)(CH-t-Bu).[4]

Molybdenum difluoride dioxide exists as a sublimable white solid, in contrast to the dichloride.

References
  1. Ward, Brian G.; Stafford, Fred E. (1968). "Synthesis and Structure of Four- and Five-Coordinated Gaseous Oxohalides of Molybdenum(VI) and Tungsten(VI)". Inorganic Chemistry. 7 (12): 2569–2573. doi:10.1021/ic50070a020.
  2. Francisco J. Arnaiz (1997). "Dichlorodioxobis(Dimethylsulphoxide)-Molybdenum(VI)". Dichlorodioxobis(Dimethylsulphoxide) Molybdenum(VI). Inorganic Syntheses. Vol. 31. pp. 246–7. doi:10.1002/9780470132623.ch39. ISBN 978-0-470-13262-3.
  3. Gibson, V. C.; Kee, T. P.; Shaw, A. (1988). "New, improved synthesis of the group 6 oxyhalides, W(O)Cl4, W(O)2Cl2 and Mo(O)2Cl2". Polyhedron. 7 (7): 579–80. doi:10.1016/S0277-5387(00)86336-6.
  4. Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. (1990). "Synthesis of molybdenum imido alkylidene complexes and some Reactions Involving Acyclic Olefins". Journal of the American Chemical Society. 112 (10): 3875–3886. doi:10.1021/ja00166a023.
  5. Takahashi, Hideyuki (14 January 2021). "Method of producing high bulk density molybdenum oxychloride".
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