Molybdenum(III) chloride
{{chembox
| verifiedrevid = 428807101
| Name = Molybdenum(III) chloride
| ImageFileL1 = Alpha-MoCl3.png
| ImageSizeL1 = 135
| ImageCaptionL1 = α-MoCl3
| ImageNameL1 = Molybdenum(III) chloride alpha polymorph
| ImageFileR1 = MoCl3.png
| ImageSizeR1 =
| ImageCaptionR1 = β-MoCl3
| ImageNameR1 = Molybdenum(III) chloride beta polymorph
| IUPACName = Molybdenum(III) chloride
Molybdenum trichloride
| OtherNames =
|Section1={{Chembox Identifiers
| CASNo = 13478-18-7
| CASNo_Ref = {{cascite|correct|CAS}}
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 9D9PY7688B
| RTECS =
| PubChem = 83515
| ChemSpiderID = 75350
| InChI = 1/3ClH.Mo/h3*1H;/q;;;+3/p-3
| InChIKey = ZSSVQAGPXAAOPV-DFZHHIFOAN
| StdInChI = 1S/3ClH.Mo/h3*1H;/q;;;+3/p-3
| StdInChIKey = ZSSVQAGPXAAOPV-UHFFFAOYSA-K
| EINECS = 236-775-9
| SMILES = Cl[Mo](Cl)Cl
}}
|Section2={{Chembox Properties
| Formula = MoCl3
| MolarMass = 202.30 g/mol
| Appearance = dark red solid
paramagnetic
| Density = 3.58 g/cm3
| Solubility = insoluble
| SolubleOther = insoluble in ethanol, diethyl ether
| MeltingPtC = 410
| MeltingPt_notes = (decomposes)
| BoilingPtC =
| MagSus = +43.0·10−6 cm3/mol
}}
|Section3={{Chembox Structure
| Coordination =
| CrystalStruct =
| Dipole =
}}
|Section7={{Chembox Hazards
| ExternalSDS =
| MainHazards =
| FlashPt = Non-flammable
}}
|Section8={{Chembox Related
| OtherAnions = Molybdenum(III) fluoride
Molybdenum(III) bromide
Molybdenum(III) iodide
| OtherCations = Chromium(IV) chloride
Tungsten(V) chloride
| OtherFunction = Molybdenum(II) chloride
Molybdenum(IV) chloride
Molybdenum(V) chloride
| OtherFunction_label = molybdenum chlorides
}}
}}
Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals.{{Cite book |last=Perry |first=Dale L. | name-list-style = vanc |title=Handbook of Inorganic Compounds|publisher=Taylor & Francis|year=2011|isbn=978-1-4398-1461-1|edition=2nd|location=Boca Raton|pages=279}}
Synthesis and structure
Molybdenum(III) chloride is synthesized by the reduction of molybdenum(V) chloride with hydrogen.{{cite journal | vauthors = Couch DE, Brenner A | title = Preparation of Trichloride and Tetrachloride of Molybdenum | journal = Journal of Research of the National Bureau of Standards Section A | volume = 63A | issue = 2 | pages = 185–188 | date = 1959 | pmid = 31216151 | pmc = 5287202 | doi = 10.6028/jres.063A.013 }} A higher yield is produced by the reduction of pure molybdenum(V) chloride with anhydrous tin(II) chloride as the reducing agent.{{cite book |last=Larson |first=Melvin L. | name-list-style = vanc|title=Inorganic Syntheses |volume=12|year=1970|pages=178–181|chapter=Preparation of Some Metal Halides- Anhydrous Molybdenum Halides and Oxide Halides - A Summary}}
Molybdenum trichloride exists as two polymorphs: alpha (α) and beta (β). The alpha structure is similar to that of aluminum chloride (AlCl3). In this structure, molybdenum has octahedral coordination geometry and exhibits cubic close-packing in its crystalline structure. The beta structure, however, exhibits hexagonal close packing.{{Cite journal| vauthors = Hillebrecht H, Schmidt PJ, Rotter HW, Thiele G, Zönnchen P, Bengel H, Cantow HJ, Magonov SN, Whangbo MH | title = Structural and scanning microscopy studies of layered compounds MCl3 (M= Mo, Ru, Cr) and MOCl2 (M= V, Nb, Mo, Ru, Os) |journal=Journal of Alloys and Compounds |year = 1997|volume=246|issue=1–2 | pages=70–79 |doi=10.1016/S0925-8388(96)02465-6 }}
Ether complexes
Molybdenum trichloride gives a ether complexes MoCl3(thf)3 and MoCl3(Et2O)3. They are beige, paramagnetic solids. Both feature octahedral Mo centers. The diethyl ether complex is synthesized by reducing a Et2O solution of MoCl5 with tin powder.{{cite book |doi=10.1002/9781118744994.ch03|chapter=Ether Complexes of Molybdenum(III) and Molybdenum(IV) chlorides |series=Inorganic Syntheses |year=2014 |last1=Maria |first1=Sébastien |last2=Poli |first2=Rinaldo |title=Inorganic Syntheses: Volume 36 |pages=15–18|volume=36 |isbn=9781118744994 |url=https://hal.archives-ouvertes.fr/hal-02042499/file/332-10.1002-9781118744994.ch03-Accepted.pdf }} Older procedures involve stepwise reduction involving isolation of the Mo(IV)-thf complex.{{cite book |volume = 28 | chapter = The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes | year = 1990 |doi=10.1002/9780470132593.ch7| last1 = Dilworth | first1 = Jonathan R. | last2 = Richards | first2 = Raymond L. | title = Inorganic Syntheses | series = Inorganic Syntheses | pages = 33–43| isbn = 9780470132593 }}
Hexa(tert-butoxy)dimolybdenum(III) is prepared by the salt metathesis reaction from MoCl3(thf)3:{{cite book |doi=10.1002/9781118744994.ch18|chapter=Dimolybdenum and Ditungsten Hexa(Alkoxides)|volume=36|year=2014|last1=Broderick|first1=Erin M.|last2=Browne|first2=Samuel C.|last3=Johnson|first3=Marc J. A.|title= Inorganic Syntheses: Volume 36|series=Inorganic Syntheses|pages=95–102|isbn=9781118744994}}
:2 MoCl3(thf)3 + 6 LiOBu-t → Mo2(OBu-t)6 + 6 LiCl + 6 thf
References
{{Reflist}}
{{molybdenum compounds}}
{{Chlorides}}