Molybdenum dichloride dioxide
{{Chembox
| ImageFile = MoO2Cl2.svg
| ImageSize = 120
| ImageAlt =
| IUPACName =
| OtherNames =
|Section1={{Chembox Identifiers
| CASNo = 13637-68-8
| CASNo_Ref = {{Cascite|correct|CAS}}
| ChemSpiderID = 11252244
| EINECS = 629-286-0
| PubChem = 86628431
| InChI=1S/2ClH.Mo.2O/h2*1H;;;/q;;+2;;/p-2
| InChIKey=JCFNAADCQWXIJD-UHFFFAOYSA-L
| SMILES =[Mo](Cl)(Cl)(=O)=O
}}
|Section2={{Chembox Properties
| Formula = {{chem2|MoO2Cl2}}
| Mo=1|Cl=2|O=2
| Appearance = yellow or cream solid
| Density =
| MeltingPtC = 175
| BoilingPtC =
| Solubility = }}
|Section3={{Chembox Hazards
| GHS_ref=[https://echa.europa.eu/information-on-chemicals/cl-inventory-database/-/discli/details/162191]
| GHSPictograms = {{GHS05}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|314}}
| PPhrases = {{P-phrases|}}
| MainHazards =
| FlashPt =
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| Section9 = {{Chembox Related
| OtherCompounds = {{ubl|Molybdenum difluoride dioxide|Molybdenum oxytetrachloride|Molybdenum(VI) chloride|Uranyl chloride}}
}}
}}
Molybdenum dichloride dioxide is the inorganic compound with the formula {{chem2|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.
Structure
Gaseous molybdenum dichloride dioxide is a monomer,{{cite journal |doi=10.1021/ic50070a020 |title=Synthesis and Structure of Four- and Five-Coordinated Gaseous Oxohalides of Molybdenum(VI) and Tungsten(VI) |year=1968 |last1=Ward |first1=Brian G. |last2=Stafford |first2=Fred E. |journal=Inorganic Chemistry |volume=7 |issue=12 |pages=2569–2573}} 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:{{cite book|series=Inorganic Syntheses|title=Dichlorodioxobis(Dimethylsulphoxide) Molybdenum(VI)|author=Francisco J. Arnaiz |chapter=Dichlorodioxobis(Dimethylsulphoxide)-Molybdenum(VI)|year=1997|volume=31|pages=246–7|doi=10.1002/9780470132623.ch39|isbn=978-0-470-13262-3}}
:MoO3 + 2 HCl → MoO2Cl2 + H2O
MoO2Cl2 can also be prepared from MoOCl4:{{cite journal |author1=Gibson, V. C. |author2=Kee, T. P. |author3=Shaw, A. | title = New, improved synthesis of the group 6 oxyhalides, W(O)Cl4, W(O)2Cl2 and Mo(O)2Cl2 | journal = Polyhedron | year = 1988 | volume = 7 | issue = 7 | pages = 579–80 | doi = 10.1016/S0277-5387(00)86336-6}}
:MoOCl4 + O(Si(CH3)3)2 → MoO2Cl2 + 2 ClSi(CH3)3
It is also prepared by chlorination of molybdenum dioxide:
:MoO2 + Cl2 → MoO2Cl2
It is also prepared by chlorination of molybdenum trixoide:{{cite web |last1=Takahashi |first1=Hideyuki |title=Method of producing high bulk density molybdenum oxychloride |url=https://patents.google.com/patent/US20210009436A1/en |date=14 January 2021}}
:MoO3 + Cl2 → MoO2Cl2
Reactions
Many bisadducts are known of the type {{chem2|MoO2Cl2(ether)2}}. These octahedral molecular complexes are soluble in organic solvents.
With bulky anilines, it converts to the diimido complex {{chem2|MoCl2(\dN\sAr)2(dimethoxyethane)}}. This complex is the precursor to the Schrock carbenes of the type {{chem2|Mo(OR)2(\dN\sAr)(\dCH\stBu)}}.{{cite journal|author1=Schrock, R. R. |author2=Murdzek, J. S. |author3=Bazan, G. C. |author4=Robbins, J. |author5=DiMare, M. |author6=O'Regan, M. |title=Synthesis of molybdenum imido alkylidene complexes and some Reactions Involving Acyclic Olefins|journal=Journal of the American Chemical Society|year=1990|volume=112|issue=10|pages=3875–3886|doi=10.1021/ja00166a023|bibcode=1990JAChS.112.3875S}}
Related compounds
Molybdenum difluoride dioxide exists as a sublimable white solid, in contrast to the dichloride.