Indium(III) chloride

Indium(III) chloride
	; Anhydrous
	; Tetrahydrate
Names
	Other names Indium chloride; Indium trichloride
Identifiers
CAS Number	10025-82-8 ;
3D model (JSmol)	Interactive image;
ChemSpider	23197 ;
ECHA InfoCard	100.030.027
EC Number	233-043-0;
PubChem CID	24812;
RTECS number	NL1400000;
UNII	31JB8MKF8Z ;
UN number	3260
CompTox Dashboard (EPA)	DTXSID8033566 ;
	InChI InChI=1S/3ClH.In/h31H;/q;;;+3/p-3 Key: PSCMQHVBLHHWTO-UHFFFAOYSA-K ; InChI=1/3ClH.In/h31H;/q;;;+3/p-3 Key: PSCMQHVBLHHWTO-DFZHHIFOAF;
	SMILES Cl[In](Cl)Cl;
Properties
Chemical formula	InCl3
Molar mass	221.18 g/mol
Appearance	white flakes
Density	3.46 g/cm3
Melting point	586 °C (1,087 °F; 859 K)
Boiling point	800 °C (1,470 °F; 1,070 K)
Solubility in water	195 g/100 mL, exothermic
Solubility in other solvents	THF, Ethanol
Structure
Crystal structure	Monoclinic, mS16
Space group	C12/m1, No. 12
Hazards
	Occupational safety and health (OHS/OSH):
Main hazards	Corrosive
	GHS labelling:
Pictograms
Signal word	Danger
Hazard statements	H302, H314
Precautionary statements	P260, P301+P330+P331, P303+P361+P353, P305+P351+P338, P405, P501
NFPA 704 (fire diamond)	2 0 0
Safety data sheet (SDS)	External SDS
Related compounds
Other anions	Indium(III) fluoride; Indium(III) bromide; Indium(III) iodide
Other cations	Aluminium chloride; Gallium trichloride; Thallium(III) chloride
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Indium(III) chloride is the chemical compound with the formula In Cl₃ which forms a tetrahydrate. This salt is a white, flaky solid with applications in organic synthesis as a Lewis acid. It is also the most available soluble derivative of indium.^[2] This is one of three known indium chlorides.

Synthesis and structure

Being a relatively electropositive metal, indium reacts quickly with chlorine to give the trichloride. Indium trichloride is very soluble and deliquescent.^[3] A synthesis has been reported using an electrochemical cell in a mixed methanol-benzene solution.^[4]

Like AlCl₃ and TlCl₃, InCl₃ crystallizes as a layered structure consisting of a close-packed chloride arrangement containing layers of octahedrally coordinated In(III) centers,^[5] a structure akin to that seen in YCl₃.^[6] In contrast, GaCl₃ crystallizes as dimers containing Ga₂Cl₆.^[6] Molten InCl₃ conducts electricity,^[5] whereas AlCl₃ does not as it converts to the molecular dimer, Al₂Cl₆.^[7]

Reactions

InCl₃ is a Lewis acid and forms complexes with donor ligands, L, InCl₃L, InCl₃L₂, InCl₃L₃. For example, with the chloride ion it forms tetrahedral InCl₄⁻, trigonal bipyramidal InCl₅²⁻, and octahedral InCl₆³⁻.^[5]

In diethyl ether solution, InCl₃ reacts with lithium hydride, LiH, to form ${\ce {LiInH4}}$ . This unstable compound decomposes below 0 °C,^[8] and is reacted in situ in organic synthesis as a reducing agent^[9] and to prepare tertiary amine and phosphine complexes of InH₃.^[10]

Trimethylindium, InMe₃, can be produced by reacting InCl₃ in diethyl ether solution either with the Grignard reagent ${\ce {MeMgI}}$ or methyllithium, LiMe. Triethylindium can be prepared in a similar fashion but with the grignard reagent EtMgBr.^[11]

{\ce {{InCl3}+ 3LiMe -> {Me3In.OEt2}+ 3LiCl}}

{\ce {{InCl3}+ 3MeMgI -> {Me3In.OEt2}+ 3MgClI}}

{\ce {{InCl3}+ 3EtMgBr -> {Et3In.OEt2}+ 3MgBr2}}

InCl₃ reacts with indium metal at high temperature to form the lower valent indium chlorides In₅Cl₉, In₂Cl₃ and InCl.^[5]

Catalyst in chemistry

Indium chloride is a Lewis acid catalyst in organic reactions such as Friedel-Crafts acylations and Diels-Alder reactions. As an example of the latter,^[12] the reaction proceeds at room temperature, with 1 mole% catalyst loading in an acetonitrile-water solvent mixture. The first step is a Knoevenagel condensation between the barbituric acid and the aldehyde; the second step is a reverse electron-demand Diels-Alder reaction, which is a multicomponent reaction of N,N'-dimethyl-barbituric acid, benzaldehyde and ethyl vinyl ether. With the catalyst, the reported chemical yield is 90% and the percentage trans isomer is 70%. Without the catalyst added, the yield drops to 65% with 50% trans product.

Indium chloride application, reaction product is mixture of cis-trans isomers

References

^ ^a ^b ^c ^d "Indium(III) Chloride". American Elements. Retrieved May 15, 2019.
^ Araki, S.; Hirashita, T. "Indium trichloride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289X.
^ Indium Trichloride
^ Habeeb, J. J.; Tuck, D. G. "Electrochemical Synthesis of Indium(III) Complexes" Inorganic Syntheses, 1979, volume XIX, ISBN 0-471-04542-X
^ ^a ^b ^c ^d Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0123526515
^ ^a ^b Wells, A.F. Structural Inorganic Chemistry, Oxford: Clarendon Press, 1984. ISBN 0-19-855370-6.
^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
^ Anthony John Downs (1993). Chemistry of aluminium, gallium, indium, and thallium. Springer. ISBN 0-7514-0103-X.
^ Main Group Metals in Organic Synthesis vol 1, ed. Hisashi Yamamoto, Koichiro Oshima, Wiley VCH, 2004, ISBN 3527305084
^ The Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities, Simon Aldridge, Anthony J. Downs, Wiley, 2011, ISBN 978-0-470-68191-6
^ Main Group compounds in Inorganic Syntheses, vol 31, By Schultz, Neumayer, Marks; Ed., Alan H. Cowley, John Wiley & Sons, Inc., 1997, ISBN 0471152889
^ An efficient synthesis of novel pyrano[2,3-d]- and furopyrano[2,3-d]pyrimidines via Indium-Catalyzed Multicomponent Domino Reaction Prajapati, D. Mukut Gohain, M. Beilstein Journal of Organic Chemistry 2006, 2:11 doi:10.1186/1860-5397-2-11

[sds-1] "Indium(III) Chloride". American Elements. Retrieved May 15, 2019.

[2] Araki, S.; Hirashita, T. "Indium trichloride" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289X.

[3] Indium Trichloride

[4] Habeeb, J. J.; Tuck, D. G. "Electrochemical Synthesis of Indium(III) Complexes" Inorganic Syntheses, 1979, volume XIX, ISBN 0-471-04542-X

[Wiberg&Holleman-5] Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0123526515

[Wells-6] Wells, A.F. Structural Inorganic Chemistry, Oxford: Clarendon Press, 1984. ISBN 0-19-855370-6.

[Greenwood&Earnshaw-7] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.

[downs-8] Anthony John Downs (1993). Chemistry of aluminium, gallium, indium, and thallium. Springer. ISBN 0-7514-0103-X.

[9] Main Group Metals in Organic Synthesis vol 1, ed. Hisashi Yamamoto, Koichiro Oshima, Wiley VCH, 2004, ISBN 3527305084

[10] The Group 13 Metals Aluminium, Gallium, Indium and Thallium: Chemical Patterns and Peculiarities, Simon Aldridge, Anthony J. Downs, Wiley, 2011, ISBN 978-0-470-68191-6

[11] Main Group compounds in Inorganic Syntheses, vol 31, By Schultz, Neumayer, Marks; Ed., Alan H. Cowley, John Wiley & Sons, Inc., 1997, ISBN 0471152889

[12] An efficient synthesis of novel pyrano[2,3-d]- and furopyrano[2,3-d]pyrimidines via Indium-Catalyzed Multicomponent Domino Reaction Prajapati, D. Mukut Gohain, M. Beilstein Journal of Organic Chemistry 2006, 2:11 doi:10.1186/1860-5397-2-11

[1]