Titanium tetrabromide: Difference between revisions

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	{{chembox		{{chembox
			\| Watchedfields = changed
	\| verifiedrevid = ~~381694959~~		\| verifiedrevid = 428093946
	\| Name = Titanium tetrabromide		\| Name = Titanium tetrabromide
	\| ImageFile = TiBr4.png		\| ImageFile = TiBr4.png
	<!-- \| ImageSize = 120px -->
	\| ImageName = Titanium tetrabromide		\| ImageName = Titanium tetrabromide
	\| ImageFile1 = Titanium-tetrabromide-3D-balls.png		\| ImageFile1 = Titanium-tetrabromide-3D-balls.png
		⚫	\| ImageName1 = Ball-and-stick model of the titanium tetrabromide molecule
	<!-- \| ImageSize1 = 120px -->
		⚫	\| IUPACName = Titanium(IV) bromide
⚫	\| ImageName1 = Ball-and-stick model of the titanium tetrabromide molecule
	\| ~~IUPACName~~ = Titanium tetrabromide		\| OtherNames = Titanium tetrabromide
		⚫	\|Section1={{Chembox Identifiers
⚫	\| ~~OtherNames~~ = Titanium(IV) bromide
			\| CASNo_Ref = {{cascite\|correct\|??}}
⚫	\| Section1 = {{Chembox Identifiers
	\| CASNo = 7789-68-6		\| CASNo = 7789-68-6
			\| UNII_Ref = {{fdacite\|correct\|FDA}}
⚫	\| PubChem = 123263
	\| ~~RTECS~~ =		\| UNII = 1CBW950X1W
		⚫	\| PubChem = 123263
			\| RTECS =
			\| EINECS = 232-185-0
			\| StdInChI = 1S/4BrH.Ti/h4*1H;/q;;;;+4/p-4
			\| StdInChIKey = UBZYKBZMAMTNKW-UHFFFAOYSA-J
			\| SMILES = (Br)(Br)(Br)Br
	}}		}}
	\| Section2 = {{Chembox Properties		\|Section2={{Chembox Properties
	\| Formula = TiBr<sub>4</sub>		\| Formula = TiBr<sub>4</sub>
	\| MolarMass = 367.48 g/mol		\| MolarMass = 367.483 g/mol
	\| Appearance = brown crystals <br> ]		\| Appearance = brown crystals <br> ]
	\| Density = 3.25 g/cm<sup>3</sup>		\| Density = 3.25 g/cm<sup>3</sup>
	\| Solubility = ~~decomposition~~		\| Solubility = hydrolyses
	\| Solvent = other solvents		\| Solvent = other solvents
	\| SolubleOther = chlorocarbons, benzene		\| SolubleOther = chlorocarbons, benzene
	\| ~~MeltingPt~~ = 39 °C		\| MeltingPtC = 39
	\| ~~BoilingPt~~ = 230 °C		\| BoilingPtC = 230
	}}		}}
	\| Section3 = {{Chembox Structure		\|Section3={{Chembox Structure
	\| Coordination = Tetrahedral		\| Coordination = Tetrahedral
	\| CrystalStruct = cubic, Pa<sub>3</sub>, Z = 8		\| CrystalStruct = cubic, Pa<sub>3</sub>, Z = 8
	\| Dipole = 0 ]		\| Dipole = 0 ]
	}}		}}
	\| Section7 = {{Chembox Hazards		\|Section7={{Chembox Hazards
	\| ~~ExternalMSDS~~ =		\| ExternalSDS =
	\| MainHazards = corrosive		\| MainHazards = corrosive
	\| NFPA-H = 3		\| NFPA-H = 3
	\| NFPA-F = 0		\| NFPA-F = 0
	\| NFPA-R = 1		\| NFPA-R = 1
	\| NFPA-O =		\| NFPA-S =
	\| FlashPt = ~~nonflammable~~		\| FlashPt = Non-flammable
			\| GHS_ref=<ref>{{cite web \|title=Titanium tetrabromide \|url=https://pubchem.ncbi.nlm.nih.gov/compound/123263#section=Safety-and-Hazards \|website=pubchem.ncbi.nlm.nih.gov \|access-date=12 December 2021 \|language=en}}</ref>
	\| RPhrases = 14-34
			\| GHSPictograms = {{GHS05}}
	\| SPhrases = 26-36/37/39-45
			\| GHSSignalWord = Danger
			\| HPhrases = {{H-phrases\|314}}
			\| PPhrases = {{P-phrases\|260\|264\|280\|301+330+331\|303+361+353\|304+340\|305+351+338\|310\|363\|405}}
	}}		}}
	\| Section8 = {{Chembox Related		\|Section8={{Chembox Related
	\| OtherAnions = ]<br />]		\| OtherAnions = ] <br/> ] <br/> ]
			\| OtherCompounds = ]
	\| OtherCations = ]
	\| OtherCpds = ]<br />]
	}}		}}
	}}		}}

	'''Titanium tetrabromide''' is the ] with the ] TiBr<sub>4</sub>. It is the most volatile transition metal bromide. The properties of TiBr<sub>4</sub> are an average of TiCl<sub>4</sub> and TiI<sub>4</sub>. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr<sub>4</sub> is diamagnetic, reflecting the d<sup>0</sup> configuration of the metal centre.<ref>Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.</ref>		'''Titanium tetrabromide''' is the ] with the ] TiBr<sub>4</sub>. It is the most volatile transition metal bromide. The properties of TiBr<sub>4</sub> are an average of TiCl<sub>4</sub> and TiI<sub>4</sub>. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr<sub>4</sub> is diamagnetic, reflecting the d<sup>0</sup> configuration of the metal centre.<ref>Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. {{ISBN\|0-12-352651-5}}.</ref>

	==Preparation and structure==		==Preparation and structure==
	This four-coordinated complex adopts a tetrahedral geometry. It can be prepared via several methods: (i) from the elements, (ii) via the reaction of TiO<sub>2</sub> with carbon and bromine (see ]), and (iii) by treatment of TiCl<sub>4</sub> with HBr.		This four-coordinated complex adopts a tetrahedral geometry. It can be prepared via several methods: (i) from the elements, (ii) via the reaction of TiO<sub>2</sub> with carbon and bromine (see ]), and (iii) by treatment of TiCl<sub>4</sub> with ].

	==Reactions==		==Reactions==
	~~TiBr<sub>4</sub>~~ forms adducts such as TiBr<sub>4</sub>(])<sub>2</sub> and <sup>-</sup>.<ref>{{cite journal \| journal = ] \| year = 1975 \| issue = 14 \| pages = 1402–1405 \| doi = 10.1039/DT9750001402 \| title =Pentachloro- and pentabromo-titanate(IV) ions \| ~~author~~ = Colin S. Creaser ~~and~~ J. Alan Creighton}}</ref> With bulky donor ligands, such as 2-methylpyridine (2-Mepy), five-coordinated adducts form. TiBr<sub>4</sub>(2-MePy) is trigonal bipyramidal with the pyridine in the equatorial plane.<ref>{{cite journal \| ~~author~~ = Hensen, K.; Lemke, A.; Bolte, M. \| title = Tetrabromo(2-methylpyridine-N)-titanate(IV) \| journal = ] \| year = 2000 \| volume = C56 \| issue = 12 \| pages = ~~e565 - e566~~ \| doi = 10.1107/S0108270100015407}}</ref>		Titanium tetrabromide forms adducts such as TiBr<sub>4</sub>(])<sub>2</sub> and <sup>−</sup>.<ref>{{cite journal \| journal = ] \| year = 1975 \| issue = 14 \| pages = 1402–1405 \| doi = 10.1039/DT9750001402 \| title =Pentachloro- and pentabromo-titanate(IV) ions \|author1=Colin S. Creaser \|author2=J. Alan Creighton \|name-list-style=amp }}</ref> With bulky donor ligands, such as ] (2-Mepy), five-coordinated adducts form. TiBr<sub>4</sub>(2-MePy) is trigonal bipyramidal with the pyridine in the equatorial plane.<ref>{{cite journal \|author1=Hensen, K. \|author2=Lemke, A. \|author3=Bolte, M. \| title = Tetrabromo(2-methylpyridine-N)-titanate(IV) \| journal = ] \| year = 2000 \| volume = C56 \| issue = 12 \| pages = e565–e566 \| doi = 10.1107/S0108270100015407\|bibcode=2000AcCrC..56E.565H }}</ref>

	TiBr<sub>4</sub> has been used as a Lewis-acid ] in ].<ref>{{cite journal \| ~~author~~ = B. Patterson, S. Marumoto ~~and~~ S. D. Rychnovsky \| title = Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations \| year = 2003 \| journal = ] \| volume = 5 \| issue = 17 \| pages = 3163–3166 \| doi = 10.1021/ol035303n \| pmid = 12917007}}</ref>		TiBr<sub>4</sub> has been used as a Lewis-acid ] in ].<ref>{{cite journal \|author1=B. Patterson, S. Marumoto \|author2=S. D. Rychnovsky \|name-list-style=amp \| title = Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations \| year = 2003 \| journal = ] \| volume = 5 \| issue = 17 \| pages = 3163–3166 \| doi = 10.1021/ol035303n \| pmid = 12917007}}</ref>

	~~TiBr<sub>4</sub>~~ ~~reacts~~ ~~rapidly~~ ~~with~~ ~~TiCl<sub>4</sub>~~ to give a statistical mixture of the tetrahalides, TiBr<sub>~~4-x~~</sub>Cl<sub>x</sub> (x = 0-4). The mechanism of this ~~exchange~~ is a ~~matter~~ of ~~some~~ ~~dispute; a~~ ~~reasonable~~ pathway ~~involves~~ the intermediacy of ]s.<ref>{{cite journal \| ~~author~~ = S. P. Webb ~~and~~ M. S. Gordon \| title = Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br) \| year = 1999 \| journal = ] \| volume = 121 \| issue = 11 \| pages = 2552–2560 \| doi = 10.1021/ja983339i}}</ref>		The tetrabromide and tetrachlorides of titanium react to give a statistical mixture of the mixed tetrahalides, TiBr<sub>4−x</sub>Cl<sub>x</sub> (x = 0-4). The mechanism of this ] is uncertain. One proposed pathway invokes the intermediacy of ]s.<ref>{{cite journal \|author1=S. P. Webb \|author2=M. S. Gordon \|name-list-style=amp \| title = Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br) \| year = 1999 \| journal = ] \| volume = 121 \| issue = 11 \| pages = 2552–2560 \| doi = 10.1021/ja983339i\| url = https://lib.dr.iastate.edu/cgi/viewcontent.cgi?article=1355&context=chem_pubs }}</ref>

	==Safety==		==Safety==
	TiBr<sub>4</sub> hydrolyzes rapidly, potentially dangerously, to release ].		TiBr<sub>4</sub> hydrolyzes rapidly, potentially dangerously, to release ], otherwise known as hydrobromic acid.

	==References==		==References==
	{{reflist}}		{{reflist}}

	{{Titanium compounds}}		{{Titanium compounds}}
			{{bromine compounds}}

	]		]
	]		]
			]

Latest revision as of 02:59, 19 February 2024

Titanium tetrabromide
Names


IUPAC name Titanium(IV) bromide
Other names Titanium tetrabromide
Identifiers
CAS Number	7789-68-6
3D model (JSmol)	Interactive image
ECHA InfoCard	100.029.259
EC Number	232-185-0
PubChem CID	123263
UNII	1CBW950X1W
CompTox Dashboard (EPA)	DTXSID90894990
InChI InChI=1S/4BrH.Ti/h4*1H;/q;;;;+4/p-4Key: UBZYKBZMAMTNKW-UHFFFAOYSA-J
SMILES (Br)(Br)(Br)Br
Properties
Chemical formula	TiBr₄
Molar mass	367.483 g/mol
Appearance	brown crystals hygroscopic
Density	3.25 g/cm
Melting point	39 °C (102 °F; 312 K)
Boiling point	230 °C (446 °F; 503 K)
Solubility in water	hydrolyses
Solubility in other solvents	chlorocarbons, benzene
Structure
Crystal structure	cubic, Pa₃, Z = 8
Coordination geometry	Tetrahedral
Dipole moment	0 D
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	corrosive
GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H314
Precautionary statements	P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P363, P405
NFPA 704 (fire diamond)	3 0 1
Flash point	Non-flammable
Related compounds
Other anions	Titanium(IV) chloride Titanium(IV) fluoride Titanium(IV) iodide
Related compounds	Titanium(III) bromide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). Y verify (what is ?) Infobox references

Chemical compound

Titanium tetrabromide is the chemical compound with the formula TiBr₄. It is the most volatile transition metal bromide. The properties of TiBr₄ are an average of TiCl₄ and TiI₄. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr₄ is diamagnetic, reflecting the d configuration of the metal centre.

Preparation and structure

This four-coordinated complex adopts a tetrahedral geometry. It can be prepared via several methods: (i) from the elements, (ii) via the reaction of TiO₂ with carbon and bromine (see Kroll process), and (iii) by treatment of TiCl₄ with HBr.

Reactions

Titanium tetrabromide forms adducts such as TiBr₄(THF)₂ and . With bulky donor ligands, such as 2-methylpyridine (2-Mepy), five-coordinated adducts form. TiBr₄(2-MePy) is trigonal bipyramidal with the pyridine in the equatorial plane.

TiBr₄ has been used as a Lewis-acid catalyst in organic synthesis.

The tetrabromide and tetrachlorides of titanium react to give a statistical mixture of the mixed tetrahalides, TiBr_4−xCl_x (x = 0-4). The mechanism of this redistribution reaction is uncertain. One proposed pathway invokes the intermediacy of dimers.

Safety

TiBr₄ hydrolyzes rapidly, potentially dangerously, to release hydrogen bromide, otherwise known as hydrobromic acid.

References

"Titanium tetrabromide". pubchem.ncbi.nlm.nih.gov. Retrieved 12 December 2021.
Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
Colin S. Creaser & J. Alan Creighton (1975). "Pentachloro- and pentabromo-titanate(IV) ions". J. Chem. Soc., Dalton Trans. (14): 1402–1405. doi:10.1039/DT9750001402.
Hensen, K.; Lemke, A.; Bolte, M. (2000). "Tetrabromo(2-methylpyridine-N)-titanate(IV)". Acta Crystallographica. C56 (12): e565 – e566. Bibcode:2000AcCrC..56E.565H. doi:10.1107/S0108270100015407.
B. Patterson, S. Marumoto & S. D. Rychnovsky (2003). "Titanium(IV)-Promoted Mukaiyama Aldol-Prins Cyclizations". Org. Lett. 5 (17): 3163–3166. doi:10.1021/ol035303n. PMID 12917007.
S. P. Webb & M. S. Gordon (1999). "Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br)". J. Am. Chem. Soc. 121 (11): 2552–2560. doi:10.1021/ja983339i.

Titanium compounds

Titanium(II)

Organotitanium(II) compounds

Titanium(III)

Organotitanium(III) compounds	₂

Titanium(IV)

Titanate compounds	BaTiO₃ Ba₂TiO₄ Bi₄Ti₃O₁₂ CaTiO₃ CaCu₃Ti₄O₁₂ CaZrTi₂O₇ Cs₂TiO₃ Dy₂Ti₂O₇ EuBaTiO₄ FeTiO₃ Ho₂Ti₂O₇ Li₂TiO₃ MnTiO₃ Na₂Ti₃O₇ Na_0.5Bi_0.5TiO₃ Na₂TiF₆ K₂TiF₆ Li₂TiF₆ Rb₂TiF₆ NiTiO₃ PbTiO₃ Pb(Zr,Ti)O₃ SrTiO₃ ZnTiO₃
Organotitanium(IV) compounds

v t e Bromine compounds
Br(−I)	Br CH₃Br CH₂Br₂ CHBr₃ CBr₄ HBr C₃H₅Br
Br(−I,I)	Br−3
Br(I)	BrCl BrF BrN₃ BrNO₃ Br₂O BrO NBr₃
Br(II)	BrO
Br(I,V)	Br₂O₃
Br(III)	BrF₃ BrO−2
Br(IV)	BrO₂
Br(V)	BrF₅ Br₂O₅ BrO−3 BrOF₃ BrO₂F
Br(VII)	BrO−4 BrO₃F

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