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Revision as of 13:22, 15 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,074 edits Saving copy of the {{chembox}} taken from revid 472468422 of page Titanium(III)_chloride for the Chem/Drugbox validation project (updated: '').		Latest revision as of 05:08, 9 December 2024 edit 2600:100d:a0ed:1dcb:4593:961a:521a:b75f (talk) →Synthesis and reactivity
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	{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
	{{chembox		{{chembox
			| Verifiedfields = changed
⚫	| verifiedrevid = 470610971
			| Watchedfields = changed
⚫	| Name = Titanium(III) chloride
		⚫	| verifiedrevid = 477000246
		⚫	| Name = Titanium(III) chloride
	| ImageFile1 = Beta-TiCl3-chain-from-xtal-3D-balls.png		| ImageFile1 = Beta-TiCl3-chain-from-xtal-3D-balls.png
	| ImageSize1 = 250px
	| ImageName1 =		| ImageName1 =
	| ImageFileL2 = Beta-TiCl3-chains-packing-from-xtal-3D-balls-B.png		| ImageFileL2 = Beta-TiCl3-chains-packing-from-xtal-3D-balls-B.png
	| ImageSizeL2 = 120px
	| ImageCaptionL2 = β-TiCl<sub>3</sub> viewed along the chains		| ImageCaptionL2 = β-TiCl<sub>3</sub> viewed along the chains
	| ImageFileR2 = TiCl3.jpg		| ImageFileR2 = TiCl3.jpg
	| ImageSizeR2 = 120px
	| ImageCaptionR2 = TiCl<sub>3</sub> solution		| ImageCaptionR2 = TiCl<sub>3</sub> solution
	| OtherNames = titanium trichloride<br />titanous chloride		| OtherNames = titanium trichloride<br />titanous chloride
	| Section1 = {{Chembox Identifiers		|Section1={{Chembox Identifiers
	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}		| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChemSpiderID = 56398		| ChemSpiderID = 56398
	| InChI = 1/3ClH.Ti/h3*1H;/q;;;+3/p-3		| InChI = 1/3ClH.Ti/h3*1H;/q;;;+3/p-3
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	| StdInChIKey = YONPGGFAJWQGJC-UHFFFAOYSA-K		| StdInChIKey = YONPGGFAJWQGJC-UHFFFAOYSA-K
	| CASNo = 7705-07-9		| CASNo = 7705-07-9
	| CASNo_Ref = {{cascite|correct|CAS}}		| CASNo_Ref = {{cascite|correct|CAS}}
			| UNII_Ref = {{fdacite|changed|FDA}}
⚫	| PubChem = 62646
	| RTECS = XR1924000		| UNII = GVD566MM7K
		⚫	| PubChem = 62646
			| RTECS = XR1924000
			| EINECS = 231-728-9
	}}		}}
	| Section2 = {{Chembox Properties		|Section2={{Chembox Properties
	| Formula = TiCl<sub>3</sub>		| Formula = TiCl<sub>3</sub>
	| MolarMass = 154.225 g/mol		| MolarMass = 154.225 g/mol
	| Appearance = red-violet crystals <br> ]		| Appearance = red-violet crystals <br> ]
			| Density = 2.64 g/cm<sup>3</sup><ref name=":0">{{cite book | last=Eagleson | first=Mary | title=Concise encyclopedia chemistry | publisher=Walter de Gruyter | publication-place=Berlin | date=1994 | isbn=0-89925-457-8 | oclc=29029713}}</ref>
	| Density = 2.64 g/cm<sup>3</sup>
	| Solubility = very soluble		| Solubility = very soluble
	| SolubleOther = soluble in ], ], certain ]s; <br> insoluble in ] and ]s		| SolubleOther = soluble in ], ], certain ]s; <br> insoluble in ] and ]s
			| MeltingPtC = 440
	| MeltingPt = 425 °C (decomposes)
			| MeltingPt_notes = (decomposes)<ref name=":0"/>
	| BoilingPt = 960 °C
	| RefractIndex = 1.4856		| RefractIndex = 1.4856
			| MagSus = {{val|+1110.0e-6|u=cm<sup>3</sup>/mol}}
	}}		}}
	| Section7 = {{Chembox Hazards		|Section7={{Chembox Hazards
			| ExternalSDS =
	| ExternalMSDS =
	| MainHazards = Corrosive		| MainHazards = Corrosive
	| EUIndex = Not listed
	}}		}}
	| Section8 = {{Chembox Related		|Section8={{Chembox Related
	| OtherAnions = ]<br/>]<br/>]		| OtherAnions = ]<br/>]<br/>]
	| OtherCations = ]<br/>]<br/>]		| OtherCations = ]<br/>]<br/>]
	| OtherCpds = ]<br/>]		| OtherCompounds = ]<br/>]
	}}		}}
	}}		}}
			'''Titanium(III) chloride''' is the ] with the formula TiCl<sub>3</sub>. At least four distinct species have this formula; additionally ] derivatives are known. TiCl<sub>3</sub> is one of the most common halides of titanium and is an important catalyst for the manufacture of ]s.
			==Structure and bonding==
			In TiCl<sub>3</sub>, each titanium atom has one ''d'' electron, rendering its derivatives ], that is, the substance is attracted into a magnetic field. Solutions of titanium(III) chloride are violet, which arises from ] of its ]. The colour is not very intense since the transition is ] by the ].
			Four solid forms or ] of TiCl<sub>3</sub> are known. All feature titanium in an octahedral coordination sphere. These forms can be distinguished by ] as well as by their magnetic properties, which probes ]s. β-TiCl<sub>3</sub> crystallizes as brown needles. Its structure consists of chains of TiCl<sub>6</sub> octahedra that share opposite faces such that the closest Ti–Ti contact is 2.91&nbsp;Å. This short distance indicates strong metal–metal interactions (see figure in upper right). The three violet "layered" forms, named for their color and their tendency to flake, are called alpha (α), gamma (γ), and delta (δ). In α-TiCl<sub>3</sub>, the chloride ]s are ]. In γ-TiCl<sub>3</sub>, the chlorides anions are ]. Finally, disorder in shift successions, causes an intermediate between alpha and gamma structures, called the δ form. The TiCl<sub>6</sub> share edges in each form, with 3.60&nbsp;Å being the shortest distance between the titanium cations. This large distance between titanium ]s precludes direct metal-metal bonding. In contrast, the trihalides of the heavier metals ] and ] engage in metal-metal bonding. Direct Zr–Zr bonding is indicated in ]. The difference between the Zr(III) and Ti(III) materials is attributed in part to the relative radii of these metal centers.<ref>{{Greenwood&Earnshaw2nd}}</ref>
			Two hydrates of titanium(III) chloride are known, i.e. complexes containing ]s. These include the pair of ] {{chem2|Cl3 and Cl(H2O)2}}. The former is violet and the latter, with two molecules of water of crystallization, is green.<ref>{{Greenwood&Earnshaw2nd|page = 965}}</ref>
			==Synthesis and reactivity==
			TiCl<sub>3</sub> is produced usually by reduction of ]. Older reduction methods used ]:<ref name= Sherfey>{{cite book |doi=10.1002/9780470132371.ch17|chapter=Titanium(III) Chloride and Titanium(III) Bromide|year=2007|last1=Sherfey|first1=J. M.|title=Inorganic Syntheses|pages=57–61|volume=6|isbn=978-0-470-13237-1}}</ref>
			:2&nbsp;TiCl<sub>4</sub> + H<sub>2</sub> → 2&nbsp;HCl + 2&nbsp;TiCl<sub>3</sub>
			It can also be produced by the reaction of titanium metal and hot, concentrated ]; the reaction does not proceed at room temperature, as titanium is ] against most ] by a thin surface layer of ].
			:2&nbsp;Ti + 6&nbsp;HCl → 3&nbsp;H<sub>2</sub> + 2&nbsp;TiCl<sub>3</sub>
			It is conveniently reduced with ] and sold as a mixture with ], TiCl<sub>3</sub>·AlCl<sub>3</sub>. This mixture can be separated to afford TiCl<sub>3</sub>(])<sub>3</sub>.<ref>{{cite journal|last1=Jones |first1=N. A. |last2=Liddle |first2=S. T. |last3=Wilson |first3=C. |last4=Arnold |first4=P. L. |title= Titanium(III) Alkoxy-''N''-heterocyclic Carbenes and a Safe, Low-Cost Route to TiCl<sub>3</sub>(THF)<sub>3</sub>|journal= Organometallics |year= 2007|volume= 26|issue=3 |pages= 755–757|doi= 10.1021/om060486d}}</ref> The complex adopts a meridional structure.<ref>{{cite journal|last1=Handlovic |first1=M. |last2=Miklos |first2=D. |last3=Zikmund |first3=M. |title=The structure of trichlorotris(tetrahydrofuran)titanium(III) |journal=Acta Crystallographica B |date=1981 |volume=37 |issue=4 |pages=811–814 |doi=10.1107/S056774088100438X|bibcode=1981AcCrB..37..811H }}</ref> This light-blue complex TiCl<sub>3</sub>(THF)<sub>3</sub> forms when TiCl<sub>3</sub> is treated with ] (THF).<ref>{{cite book|last1=Manzer |first1=L. E.|chapter=31. Tetragtdrfuran Complexes of Selected Early Transition Metals |title= Inorganic Syntheses|series= ]|year= 1982|volume= 21|page= 137|doi=10.1002/9780470132524.ch31|isbn=978-0-471-86520-9 }}</ref>
			:TiCl<sub>3</sub> + 3 C<sub>4</sub>H<sub>8</sub>O → TiCl<sub>3</sub>(OC<sub>4</sub>H<sub>8</sub>)<sub>3</sub>
			An analogous dark green complex arises from complexation with ]. In a reaction where all ligands are exchanged, TiCl<sub>3</sub> is a precursor to the blue-colored complex ].<ref>{{cite journal |doi=10.1007/s11224-016-0864-0|title=An Historic and Scientific Study of the Properties of Metal(III) Tris-acetylacetonates|year=2017|last1=Arslan|first1=Evrim|last2=Lalancette|first2=Roger A.|last3=Bernal|first3=Ivan|journal=Structural Chemistry|volume=28|pages=201–212|s2cid=99668641}}</ref>
			The more reduced ] is prepared by the thermal ] of TiCl<sub>3</sub> at 500&nbsp;°C. The reaction is driven by the loss of volatile ]:<ref>{{cite book|last1=Holleman |first1=A. F. |last2=Wiberg |first2=E. |title=Inorganic Chemistry |publisher=Academic Press |location=San Diego, CA |date=2001 |isbn=0-12-352651-5}}{{page needed|date=February 2021}}</ref>
			:2 TiCl<sub>3</sub> → TiCl<sub>2</sub> + TiCl<sub>4</sub>
			The ternary halides, such as A<sub>3</sub>TiCl<sub>6</sub>, have structures that depend on the cation (A<sup>+</sup>) added.<ref>{{cite journal|last1=Hinz |first1=D. |last2=Gloger |first2=T. |last3=Meyer |first3=G. |title= Ternary halides of the type A<sub>3</sub>MX<sub>6</sub>. Part 9. Crystal structures of Na<sub>3</sub>TiCl<sub>6</sub> and K<sub>3</sub>TiCl<sub>6</sub>|journal= Zeitschrift für Anorganische und Allgemeine Chemie|year= 2000 |volume= 626|pages= 822–824|doi= 10.1002/(SICI)1521-3749(200004)626:4<822::AID-ZAAC822>3.0.CO;2-6|issue= 4}}</ref> ] treated with titanium(II) chloride and ] produces crystalline CsTi<sub>2</sub>Cl<sub>7</sub>. In these structures Ti<sup>3+</sup> exhibits octahedral coordination geometry.<ref>{{cite journal|last1=Jongen |first1=L. |last2=Meyer |first2=G. |title= Caesium heptaiododititanate(III), CsTi<sub>2</sub>I<sub>7</sub>|journal= Zeitschrift für Anorganische und Allgemeine Chemie|year= 2004 |volume= 630|pages= 211–212|doi= 10.1002/zaac.200300315|issue= 2}}</ref>
			==Applications==
			TiCl<sub>3</sub> is the main ], responsible for most industrial production of ]. The catalytic activities depend strongly on the polymorph of the TiCl<sub>3</sub> (α vs. β vs. γ vs. δ) and the method of preparation.<ref>{{Ullmann|first1=Kenneth S. |last1=Whiteley |first2=T. Geoffrey |last2=Heggs |first3=Hartmut |last3=Koch |first4=Ralph L. |last4=Mawer |first5=Wolfgang |last5=Immel |title=Polyolefins |year=2005 |doi=10.1002/14356007.a21_487}}</ref>
			===Laboratory use===
			TiCl<sub>3</sub> is also a specialized ] in organic synthesis, useful for reductive coupling reactions, often in the presence of added reducing agents such as zinc. It reduces ]s to ]s.<ref>{{cite encyclopedia|first1=Lise-Lotte |last1=Gundersen |first2=Frode |last2=Rise |first3=Kjell |last3=Undheim |first4=José |last4=Méndez Andino |title=Titanium(III) Chloride |encyclopedia=] |year=2007 |doi=10.1002/047084289X.rt120.pub2|isbn=978-0-471-93623-7 }}</ref> Titanium trichloride can reduce nitrate to ammonium ion thereby allowing for the sequential analysis of nitrate and ammonia.<ref>{{cite journal|title=Determining Ammonium & Nitrate ions using a Gas Sensing Ammonia Electrode |journal=Soil and Crop Science Society of Florida |volume=65 |date=2006 |first1=D. W. |last1=Rich |first2=B. |last2=Grigg |first3=G. H. |last3=Snyder}}</ref> Slow deterioration occurs in air-exposed titanium trichloride, often resulting in erratic results, such as in reductive ]s.<ref name=OrgSyn>{{OrgSynth|year=1981|last1= Fleming|first1= Michael P.|last2= McMurry|first2=John E. |title= Reductive Coupling of Carbonyls to Alkenes: Adamantylideneadamantane|volume = 60|pages = 113|doi = 10.15227/orgsyn.060.0113}}</ref>
			==Safety==
			TiCl<sub>3</sub> and most of its complexes are typically handled under ] to prevent reactions with oxygen and moisture. Samples of TiCl<sub>3</sub> can be relatively air stable or ].<ref name="IngrahamDownes1957">{{cite journal|last1=Ingraham|first1=T. R.|last2=Downes|first2=K. W.|last3=Marier|first3=P.|title=The Production of Titanium Trichloride by Arc-Induced Hydrogen Reduction of Titanium Tetrachloride|journal=Canadian Journal of Chemistry|volume=35|issue=8|year=1957|pages=850–872|issn=0008-4042|doi=10.1139/v57-118}}</ref><ref name="Pohanish2009">{{cite book|title=Wiley Guide to Chemical Incompatibilities|last1=Pohanish |first1=Richard P. |last2=Greene |first2=Stanley A. |publisher=John Wiley & Sons|year=2009|edition=3rd|isbn=978-0-470-52330-8|page=1010}}</ref>
			==References==
			{{reflist|30em}}
			{{Titanium compounds}}
			{{Chlorides}}
			]
			]
			]
			]