7727-15-3

Usage

Uses

Used in Organic Synthesis:
Aluminum bromide is used as a catalyst in organic synthesis for facilitating various reactions such as isomerization and alkylation. Its ability to act as a Lewis acid makes it a valuable component in the synthesis of complex organic molecules.
Used in Dye Production:
In the dye industry, aluminum bromide is utilized as a catalyst for the production of various dyes. Its catalytic properties enable the synthesis of a wide range of dyes with different color characteristics and properties.
Used in Pharmaceutical Production:
Aluminum bromide is employed in the pharmaceutical industry as a catalyst for the synthesis of certain drugs and pharmaceutical compounds. Its reactivity and catalytic properties contribute to the efficient production of these compounds.
Safety Precautions:
Due to its hygroscopic nature, aluminum bromide must be handled with care to avoid contact with skin and mucous membranes, as it can cause severe burns. Additionally, it poses potential health and environmental hazards, necessitating strict safety measures during its handling and disposal.

InChI:InChI=1/Al.3BrH/h;3*1H/q+3;;;/p-3

Synthetic route

phenylaluminium dichloride (3530-39-0) + allyl bromide (106-95-6) → allylbenzene (300-57-2) + biphenyl (92-52-4) + aluminium bromide (7727-15-3)

Conditions	Yield
bis(η3-allyl-μ-chloropalladium(II)) In diethyl ether Ar atmosphere; stirring (20°C, 5 mole-% catalyst, 8 h);	A 94% B <1 C n/a
tetrakis(triphenylphosphine) palladium(0) In diethyl ether Ar atmosphere; stirring (20°C, 5 mole-% catalyst, 20 h);	A <1 B <1 C n/a

diphenylaluminum chloride (6591-30-6) + allyl bromide (106-95-6) → allylbenzene (300-57-2) + biphenyl (92-52-4) + aluminium bromide (7727-15-3)

Conditions	Yield
tetrakis(triphenylphosphine) palladium(0) In diethyl ether Ar atmosphere; stirring (20°C, 5 mole-% catalyst, 20 h);	A 37% B <1 C n/a

1,1-dibromomethane (74-95-3) + aluminium → ethene (74-85-1) + aluminium bromide (7727-15-3)

Bromoform (75-25-2) + aluminium → aluminium bromide (7727-15-3)

Conditions	Yield
Erhitzen des Reaktionsprodukts im Vakuum auf 200grad;

aluminum oxide (1333-84-2, 1344-28-1) → aluminium bromide (7727-15-3)

Conditions	Yield
With bromine; pyrographite In not given heating;
With bromine; pyrographite heating;
With sulfur dibromide In solid 350°C, with vaporous sulfur bromide;

aluminum oxide (1333-84-2, 1344-28-1) + disulphur dibromide (13172-31-1) → aluminium bromide (7727-15-3)

Conditions	Yield
reaction started at 350°C and accelerated by raising of temp.; excess of S2Br2 removed with HBr or nitrogen;
reaction started at 350°C and accelerated by raising of temp.; excess of S2Br2 removed with HBr or nitrogen;

bromine (7726-95-6) → aluminium bromide (7727-15-3)

Conditions	Yield
With aluminum(III) sulfate In water heating on water bath with small amt. of Br2 and H2O;
With bisilicates; carbon heating;
With carbon; silicates heating;

aluminium trinitrate (7784-27-2) + bromine (7726-95-6) → aluminium bromide (7727-15-3)

Conditions	Yield
In not given heating on water bath with small amt. of Br2;
In not given heating on water bath with small amt. of Br2;

bromine (7726-95-6) + aluminium (7429-90-5) → aluminium bromide (7727-15-3)

Conditions	Yield
In gas Al and Br2 in vac. were vaporized separately and reacted in gaseous state; distd. in vac.;
With air; water in moist air containing Br2 condensation of droplets of a soln. of AlBr3 occurs on a gray layer that has formed first;;
In neat (no solvent) start of react. by heating;;

aluminium (7429-90-5) → aluminium bromide (7727-15-3)

Conditions	Yield
With bromine reacted in the presence of AlBr3;
With bromine Al heated in combustion tube; with H2 or N2 deluted Br2 lead over Al;
With bromine Al sheet heated in combustion tube; vaporous Br2 leaded over Al; AlBr3 flowed out from tube;

ethylene dibromide (106-93-4) + aluminium (7429-90-5) → ethene (74-85-1) + aluminium bromide (7727-15-3)

Conditions	Yield
In ethylene dibromide
In ethylene dibromide

stannic bromide (7789-67-5) + aluminium (7429-90-5) → aluminium bromide (7727-15-3)

Conditions	Yield
In not given heating of Al with SnBr4 for 30 min gives AlBr3;;

tin(II) bromide + aluminium (7429-90-5) → aluminium bromide (7727-15-3)

Conditions	Yield
In neat (no solvent) reaction with SnBr2 under formation of AlBr3 above 216°C;; differentialthermoanalytic examinations;;

aluminium (7429-90-5) + mercury dibromide → mercury(I) bromide + aluminium bromide (7727-15-3) + mercury

Conditions	Yield
at higher temp.;;

AlBr3*Br4*CS2 → aluminium bromide (7727-15-3)

Conditions	Yield
byproducts: Br2, CS2; decompn. at 150°C;
byproducts: Br2, CS2; decompn. at 150°C;

2AlBr3*Br4*CS2 → CS2Br4 + aluminium bromide (7727-15-3)

Conditions	Yield
at 200°C;
at 200°C;

bromocyane (506-68-3) + aluminium (7429-90-5) → aluminium bromide (7727-15-3)

Conditions	Yield
120°C;
120°C;

zinc(II) selenide + AlSeBr → Zn2AlSe3Br + aluminium bromide (7727-15-3)

Conditions	Yield
In neat (no solvent) mixt. of the starting materials heated in evacuated sealed quartz tubes to 500-900°C; decompn. of educts ocurrs, AlBr3 sublimates off;	A 0% B n/a

phosphorus tribromide (7789-60-8) + aluminium (7429-90-5) → phosphorous + aluminium bromide (7727-15-3)

Conditions	Yield
In neat (no solvent) reaction at 100°C;;
In neat (no solvent) reaction at 100°C;;

bromine (10097-32-2) → aluminium bromide (7727-15-3)

Conditions	Yield
With sulfur introducing a vapor of a soln. of S in Br2 over Al oxide;
With S introducing a vapor of a soln. of S in Br2 over Al oxide;

AsBr4(1+)*AlBr4(1-)={AsBr4}{AlBr4} (119484-32-1) → bromine (7726-95-6) + aluminium bromide (7727-15-3) + arsenic(III) bromide (7784-33-0)

Conditions	Yield
equilibrium at room temp.;

lithium{aluminum-bromo(μ-dibromo)-tetrakis(tert-butoxy)titanate} → titanium(IV) tetrabutoxide + aluminium bromide (7727-15-3)

Conditions	Yield
With copper(l) chloride In tetrahydrofuran byproducts: Cu, LiCl; to a soln. of Ti-complex in THF at 0°C is added CuCl; pptn. of Cu, solvent is removed in vac., the residue is dissolved in toluene, pptd. LiCl is centrifuged off, the soln. is vacuum-evaporated, from the residue at 90-110°C is distilled the complex, crystn. at 20°C, elem. anal.;

{(CO)3Fe(P(C6H5)3)2Br}(1+)*AlBr4(1-)={(CO)3Fe(P(C6H5)3)2Br}AlBr4 → tricarbonyl bis(triphenylphosphine) iron (14741-34-5, 21255-52-7) + bis(triphenylphosphine)dicarbonyldibromoiron(II) (51744-69-5, 15020-31-2, 84622-99-1) + bromine (7726-95-6) + aluminium bromide (7727-15-3)

Conditions	Yield
In tetrahydrofuran	A <1 B n/a C n/a D n/a
In methanol	A <1 B n/a C n/a D n/a
In dichloromethane	A <1 B n/a C n/a D n/a

tetraiodophosphonium tetrabromoaluminate (361447-05-4) → aluminium bromide (7727-15-3) + iodine(I) bromide (7789-33-5) + phosphorous triiodide (13455-01-1)

Conditions	Yield
In carbon disulfide under N2, anaerobic and anhyd. conditions; dissolved in CS2;

dibromo[3-(dimethylamino)propyl]aluminium → aluminium(I) bromide (22359-97-3) + AlBr2 (136684-48-5) + hydrogen isocyanide (74-90-8, 6914-07-4) + aluminium bromide (7727-15-3) + dibromoaluminium hydride

Conditions	Yield
In neat (no solvent, gas phase); solid matrix byproducts: CH4, H2C=CH2, H2C=CHCH3; N2 atmosphere, high vacuum (1E-6 to 1E-7 mbar) thermolysis at 1000°C, trapping in argon at 15 K; further organic byproducts: H2C=N(CH3)2 and H2CCHCH2; IR-monitoring;

aluminum bromide fluoride → aluminium(III) fluoride (7784-18-1) + aluminium bromide (7727-15-3)

Conditions	Yield
In solid heating at 400°C;

lithium aluminium tetrahydride (16853-85-3) + non-1-ene (124-11-8) + aluminium bromide (7727-15-3) → 1-dibromoaluminiononane (180334-67-2)

Conditions	Yield
In diethyl ether; benzene Ar, LiAlH4 in ether added to benzene under stirring, most of the solvent removed, benzene and AlBr3 in benzene added, stirred at 20°C for 1 h, org. compound in benzene added dropwise under stirring, warmed to30-40°C for 5-10 min; NMR;	100%

aluminium bromide (7727-15-3) + (2-methylpropyl)lithium (920-36-5, 90269-51-5) + magnesium bromide → magnesium tetra(isobutyl)aluminate

Conditions	Yield
In hexane; toluene byproducts: LiBr; to stirred mixt. of MgBr2, AlBr3 and toluene at room temp., soln. of iso-C4H9Li in hexane added (Ar; ratio MgBr2, AlBr3, RLi: 1:2:8) within 20 min; react. for 3.0 h at 80°C; ppt. filtered off (Ar); (1)H NMR of soln.;	100%

aluminium bromide (7727-15-3) + thiophenol (108-98-5) → aluminium tribromide*ethanethiol (98772-99-7)

Conditions	Yield
In benzene under N2, dropwise addn. of thiol soln. to a suspension of AlBr3 in benzene, dissoln. of AlBr3, stirred for 15 min at room temp.; evapn. of solvent, dried in vac. at room temp. for 3h, elem. anal.;	100%

(1,1';3',1''-terphenyl)-2'-ol (2432-11-3) + aluminium bromide (7727-15-3) → aluminium tris(2,6-diphenylphenoxide)

Conditions	Yield
With tetraallyltin In benzene byproducts: SnBr4, propene; 2,6-diphenylphenol (12 equiv.) treated with AlBr3 (4 equiv.) in benzene at room temp., tetraallyltin (3 equiv.) added, stirred at room temp. for1 h, solvent evapd. in vacuo for 3 h with concomitant removal of SnBr4 and propene;	100%

methylthiol (74-93-1) + aluminium bromide (7727-15-3) → aluminium tribromide*methanethiol (98772-98-6)

Conditions	Yield
In benzene under N2, CH3SH introduced in a suspension of AlBr3 for 7 min, dissoln.of AlBr3, stirred for 15 min at room temp.; evapn. of solvent, dried in vac. at room temp. for 3h, elem. anal.;	100%

Trimethyl(methylthio)silane (3908-55-2) + aluminium bromide (7727-15-3) → aluminium tribromide*trimethylsilyl methyl sulphide (112908-14-2)

Conditions	Yield
In benzene a benzene soln. of Me3SiSMe was added dropwise under N2 to a suspn. of AlBr3 in benzene, mixt. was stirred for 15 min at room temp.; solvent was evapd.; elem. anal.;	100%

(ethylthio)trimethylsilane (5573-62-6) + aluminium bromide (7727-15-3) → aluminium tribromide*trimethylsilyl ethyl sulphide (112908-15-3)

Conditions	Yield
In benzene a benzene soln. of Me3SiSEt was added dropwise under N2 to a suspn. of AlBr3 in benzene, mixt. was stirred for 15 min at room temp.; solvent was evapd.; elem. anal.;	100%

phenylthiotrimethylsilane (4551-15-9) + aluminium bromide (7727-15-3) → aluminium tribromide*trimethylsilyl phenyl sulphide (112908-16-4)

Conditions	Yield
In benzene a benzene soln. of Me3SiSPh was added dropwise under N2 to a suspn. of AlBr3 in benzene, mixt. was stirred for 15 min at room temp.; solvent was evapd.; elem. anal.;	100%

disupersilyl aluminum bromide + aluminium bromide (7727-15-3) → supersilylaluminum dibromide (374569-92-3)

Conditions	Yield
In n-heptane Kinetics; all manipulations with exclusion of air and moisture; compd. prepd. fromAlBr3 and org. compd. reacted in molar ratio of 1:1 at room temp. for 2 4 d (yield depended on react. time); controlled by NMR; volatiles evapd. by oil pump, residue dissolved in heptane, NaBr filtered;	100%

selenium tetrabromide (7789-65-3) + aluminium bromide (7727-15-3) → tribromoselenium(IV) tetrabromoaluminate (69951-93-5)

Conditions	Yield
In neat (no solvent) Ar atm. (300 mbar); heating (150-200°C, several days);	100%
In dichloromethane addn. of AlBr3 to SeBr4, stirring (2 h); filtration (under dry N2), drying (vac.); elem. anal.;

(S)-3,3-bis(3,5-dimethylphenyl)-1-(2,4,6-trifluorophenyl)tetrahydro-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole + aluminium bromide (7727-15-3) → (S)-3,3-bis(3,5-dimethylphenyl)-1-(2,4,6-trifluorophenyl)tetrahydro-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborol-7-ium-7-yltribromoaluminate

Conditions	Yield
In dichloromethane; ethylene dibromide	100%

(S)-3,3-bis(2,3-dimethylphenyl)-1-(2,4,6-trifluorophenyl)tetrahydro-1H,3H-pyrrolo[1,2-c][1,3,2]oxazaborole + aluminium bromide (7727-15-3) → C27H27AlBBr3F3NO

Conditions	Yield
In dichloromethane; ethylene dibromide	100%

WH2(η-cyclopentadienyl)2 + aluminium bromide (7727-15-3) → bis(η5-cyclopentadienyl)tungsten dihydride * AlBr3 (79560-37-5)

Conditions	Yield
In diethyl ether stoich. amts. (pptn.);	99%

bis(tricyclohexylphosphine)platinum(0) (55664-33-0) + aluminium bromide (7727-15-3) → [(Cy3P)2Pt(AlBr3)] (960294-94-4)

Conditions	Yield
In benzene AlBr3 was added to a soln. of Pt-complex in benzene, the soln. was kept at room temp. for 24 h;	99%
In toluene (Ar); Al salt added to a soln. of Pt complex; evapd. (vac.); elem. anal.;	98%

thallium(I) bromide + aluminium bromide (7727-15-3) → Tl(1+)*AlBr4(1-)=TlAlBr4 (114064-41-4)

Conditions	Yield
In neat (no solvent, solid phase) (Ar); solid state reaction; equimolar mixt. of TlBr, and AlBr3 sealed under vac. in glass ampoules; heated with 10°C/h to 150°C for 48 h; cooled to 25°C with 2.degre.C/h; detn. by XRD;	99%

1,2-dimethoxyethane (110-71-4) + aluminium bromide (7727-15-3) → aluminium tribromide-1,2-dimethoxyethane (182561-85-9)

Conditions	Yield
In toluene (N2); stirring (1 h); filtration, washing (toluene); elem. anal.;	98.7%

aluminium bromide (7727-15-3) + sodium triethoxysilanolate (53201-03-9) → tris(triethoxysiloxy)aluminum + sodium bromide (7647-15-6)

Conditions	Yield
In benzene (glovebox); addn. of a soln. of AlBr3 in C6H6 to a soln. of silicon compd. in C6H6 in vac. with stirring, sealing, heating to 40°C for 30min with shaking; centrifugation, decantation, evapn; elem. anal.;	A 98% B 98%

(1R,2R)-(-)-N,N'-bis(3,5-di-tert-butylsalicydene)-1,2-cyclohexanediaminocobalt(II) (176763-62-5) + aluminium bromide (7727-15-3) → [AlBr3(Co((R,R)-C6H10(NCHC6H2O(tert-butyl)2)2))]

Conditions	Yield
In dichloromethane; water addn. of Co(C6H10(NCHC6H2O(t-Bu)2)2) (1 equiv.) to soln. of AlBr3 (1 equiv.) in CH2Cl2/H2O; stirring at room temp. for 1 h; concn. under reduced pressure, treatment with H2O and CH2Cl2;	98%

[(S,S)-Carbox-iPr]H + aluminium bromide (7727-15-3) → (S,S)-1,7-bis(1-bromo-3-methylbutanamide-2-yl)-1,7-dicarba-closo-dodecaborane

Conditions	Yield
With I2 In dichloromethane a mixt. of B compd., I2, and AlBr3 in CH2Cl2 refluxed for 16.5 h under N2; poured into ice-cold H2O, the org. phase sepd., the aq. layer extd. (Et2O), the combined org. phase washed (Na2S2O3 soln., then H2O), dried (MgSO4), solvent-removed, recrystd. (hexane); elem. anal.;	98%

tetrahydrofuran (109-99-9) + N,N-bis(2-hydroxy-3,5-di-tert-butylphenyl)amine (97355-16-3) + aluminium bromide (7727-15-3) → [bis(3,5-di-tert-butyl-2-phenol)amine(2-)]AlBr(THF) (1384526-06-0)

Conditions	Yield
With KH In tetrahydrofuran under inert atm. mixt. ligand and KH in THF were stirred at room temp. for 2 h, soln. was frozen, AlBr3 was added upon thawing, stirred at room temp. overnight; solvent was removed in vacuo, residue was co-evapd. with pentane; elem. anal.;	98%

dimethylacetylene (503-17-3) + aluminium bromide (7727-15-3) → C4(CH3)4*AlBr3 (70492-15-8)

Conditions	Yield
In methyl cyclohexane addn. of 2-butyne to soln. of AlBr3, 0°C, stirred 15h at 25°C, filtered, washed with methylcyclohexane, dried in vac.; elem. anal.;	97%

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + aluminium bromide (7727-15-3) → Co2(CO)8*AlBr3

Conditions	Yield
In n-heptane room temp.;	97%
In benzene room temp.;	97%
In benzene room temp.;	97%

aluminium bromide (7727-15-3) + (pentafluoro phenyl) methyl mercury (653-38-3) → (pentafluoro phenyl) dibromo alane (4457-90-3)

Conditions	Yield
In neat (no solvent) heating of the components ( molar ratio 1 : 1) in a closed tube at 70°C, 5 days;;	97%

uranium dioxide + aluminium bromide (7727-15-3) → uranium(IV) bromide (13470-20-7)

Conditions	Yield
Stage #1: uranium dioxide; aluminium bromide at 250℃; for 12h; Sealed tube; Stage #2: at 350℃; for 144h; Sealed tube;	97%

lithium aluminium tetrahydride (16853-85-3) + camphene (79-92-5) + aluminium bromide (7727-15-3) → C10H17AlBr2

Conditions	Yield
In diethyl ether; benzene Ar, LiAlH4 in ether added to benzene under stirring, most of the solvent removed, benzene and AlBr3 in benzene added, stirred at 20°C for 1 h, org. compound in benzene added drowise under stirring, warmed to 30-40°C for 5-10 min; NMR;	96%

1,3-dimethyl-2-dimethylaminodiazaborolane (26944-84-3) + aluminium bromide (7727-15-3) → 1,3-dimethyl-2-(dimethylamino)-1,3,2-diazaborolidine-1,3-bis(aluminum-tribromide)

Conditions	Yield
under N2, at -78°C; excess of Lewis-acid used; elem. anal.;	96%

2-Phenoxyethanol (122-99-6) + aluminium bromide (7727-15-3) → [(μ-2-phenoxyethanolate)AlBr2]2 (223647-11-8)

Conditions	Yield
In toluene N2-atmosphere; slow addn. of Al-salt to slight excess of alcohol at 25°C, stirring for 4 h; drying (vac.), extn. into CH2Cl2, drying (vac.); elem. anal.;	96%

potassium triethoxysilanolate (168292-74-8) + aluminium bromide (7727-15-3) → potassium tetrakis(triethoxysiloxy)aluminates + potassium bromide (7558-02-3)

Conditions	Yield
In benzene (glovebox); dropwise addn. of a soln. of AlBr3 in C6H6 to a soln. of silicon compd. in C6H6 over 15 min with stirring, refluxing for 7 h; centrifugation, decantation, evapn.; elem. anal.;	A 88% B 96%

(2,2,6,6-tetramethylpiperidino)2AlBr(isoquinoline) (211381-77-0) + aluminium bromide (7727-15-3) → (2,2,6,6-tetramethylpiperidino)2Al(isoquinoline) tetrabromoaluminate (211381-88-3)

Conditions	Yield
In Bromoform inert atmosphere, addn. of soln. of AlBr3 to soln of isoquinoline complex at 0°C, 30 min; reduction of volume, crystn. (-20°C, overnight); elem. anal.;	96%

lithium aluminium tetrahydride (16853-85-3) + 2,4-dimethyl-2-pentene (625-65-0) + aluminium bromide (7727-15-3) → (CH3)2CHCH(AlBr2)CH(CH3)CH3 (180334-71-8)

Conditions	Yield
In diethyl ether; benzene Ar, LiAlH4 in ether added to benzene under stirring, most of the solvent removed, benzene and AlBr3 in benzene added, stirred at 20°C for 1 h, org. compound in benzene added drowise under stirring, warmed to 30-40°C for 5-10 min; NMR;	96%

Upstream product

• 74-95-3 1,1-dibromomethane 
• 75-25-2 Bromoform 
• 1333-84-2 aluminum oxide 
• 13172-31-1 disulphur dibromide 
• 7726-95-6 bromine 
• 7784-27-2 aluminium trinitrate 
• 7429-90-5 aluminium 
• 106-93-4 ethylene dibromide 
• 7789-67-5 stannic bromide 
• 506-68-3 bromocyane 
• 7789-60-8 phosphorus tribromide 
• 10097-32-2 bromine 
• 119484-32-1 AsBr₄⁽¹⁺⁾*AlBr₄^(1-)={AsBr₄}{AlBr₄} 
• 3530-39-0 phenylaluminium dichloride 

Downstream Products

• 2382-96-9 benzo[d]oxazole-2-(3H)-thione 
• 99855-09-1 2-(4-ethoxyphenyl)-4,5-dihydro-1H-oxazole 
• 74-96-4 ethyl bromide 
• 75-00-3 chloroethane 
• 111-70-6 n-heptan1ol 
• 3316-09-4 1,2-dihydroxy-4-nitrobenzene 
• 15930-48-0 4,5,6,7-tetrabromo-benzo[1,3]dioxole 
• 488-47-1 Tetrabromocatechol 
• 2294-93-1 1,2,2-triphenyl-1-ethanol 
• 101-76-8 4,4'-dichlorodiphenylmethane 
• 831-81-2 4-chlorophenyl(phenyl)methane 
• 79-27-6 1,1,2,2-tetrabromoethane 
• 58169-99-6 2,3,4,6-tetrabromo-5-methyl-phenol 
• 187737-37-7 propene 

Relevant academic research and scientific papers

Vibrational spectroscopy and normal coordinate analysis of μ halo hexahalodialuminates ions Al2X7- (X = Cl, Br, I) in some salts and in Friedel-Crafts solutions

Infrared and Raman spectra are reported for (Me4N)Al2Cl7, (Et4N)Al2Cl7, KAl2Br7 and CsAl2I7 in the solid state at ordinary temperature.An assignment for practically all the vibrational modes is proposed for the three ions Al2Cl7-, Al2Br7- and Al2I7-.To elucidate the species occurring in the Friedel-Crafts liquids , the spectra of these solutions were also recorded.The quasi identity of the halogenide part of the spectra with the previous one leads to the unique formulation ArH2+Al2X7- for these solutions, in these cases the Al2X7- ion appears at a higher local symmetry of the AlX3 groups than in the solid state.An approximate valence force field calculation confirms the assignments.It also shows the transferability of force constants for a X-AlX3 model.Spectroscopic particularities are explained in terms of different coupling between bridged and terminal stretching modes.

Complex equilibria in unsaturated vapor over AlBr3

Unsaturated AlBr 3 vapor pressure was measured over the temperature and pressure ranges 560-845 K and 54-145 torr by the static method using a quartz diaphragm pressure gauge with increased sensitivity (the confidence interval of pressure, including thermal drift of zero pressure gauge point, was 0.3 torr, and that of temperature, 0.3 K). Two equilibrium models were considered, one including AlBr3 and Al2Br6 and the other, AlBr3, Al2Br6, and Al3Br 9. The molecular constants of all vapor constituents were determined using density functional theory at the B3LYP/6-31G(d,p) level. The thermodynamic functions of all bromides were calculated in the rigid rotator-harmonic oscillator approximation. The enthalpies of independent equilibria for each model were determined by minimizing the residual sum of the squares of pressure discrepancies. According to the first model, 0.5Al2Br6 = AlBr3, ΔHo(298.15) = 13629.1 ± 9 cal/mol. According to the second model, 0.5Al2Br6 = AlBr 3, ΔHo(298.15) = 13638.8 ± 8 cal/mol, and 1.5Al2Br6 = Al3Br9, ΔH o(298.15) = -8528 ± 800 cal/mol. The second model, for which the variance of pressure differs insignificantly from the experimental variance of pressure, should be given preference.

Dimeric Di(tert-butyl)haloalanes and a Monomeric Di(tert-butyl)phosphino- di(tert-butyl)alane

The di(tert-butyl)aluminum halides, tBu2AlX (X = Br, I) have been prepared in yields ranging from 55 to 64 % from AlX3 and Lit Bu in a 1: 2 molar ratio in pentane. In the crystal these pyrophoric compounds are dimeric featuring Al-X-Al bridges. The reaction of AlCI3 with LitBu in diethyl ether produced a volatile solvate of composition tBu3Al-Cl- AltBu2(OEt2). Reaction of this species with AlCl 3 at 120 °C yielded a separable mixture of tBu2AlCl and tBu2AlCl(OEt2). tBu2AlCl and tBu 2GaCl react with tBu2PLi to produce the monomeric compounds tBu2E-PtBu2 (E = Al, Ga). The aluminum compound decomposes at 111 °C to give a mixture of the cis/trans-isomers of [tBu(H) Al-PtBu2]2 while at 200 °C only the trans-isomer is formed.

Reversible bromide-chloride exchange in zirconium cluster compounds: Synthesis by means of ionic liquids, structures, and some spectral data of (EMIm)4[(Zr6Z)Br18] cluster phases (Z = Be, Fe)

The solid-state precursor cluster chlorides Na4[(Zr 6Be)Cl16] and K[(Zr6Fe)Cl15] readily dissolve in Lewis-basic ionic liquids consisting of mixtures of EMIm-Br and AlBr3 (EMIm: 1-ethyl-3-methyl-imidazolium) to give dark colored solutions. From these solutions, the cluster phases (EMIm)4[(Zr 6Fe)Br18] (1) and (EMIm)4[(Zr 6Be)Br18] (2) were obtained in acceptable yields. Crystallographic data of the isostructural phases are the following: monoclinic, P21/c, Z = 2. The data for 1 follow: a = 10.5746(4) A, b = 22.6567(9) A, and c = 13.0260(5) A, β = 111.279(2)°. The data for 2 follow: a = 10.574(2) A, b = 22.681(4) A, and c = 13.041(2) A, β = 111.31(2)°. Compound 1 is the first detailed structurally characterized molecular Fe-centered zirconium bromide cluster phase. In the bromide based ionic liquid, a complete exchange of all the outer and inner chlorides by bromide takes place. Since the inverse reaction, the exchange of all bromides by chlorides, was reported before, this complete ligand exchange can be considered as reversible, with the equilibrium being largely determined by the free ligand concentration. The electronic spectra of a chloride supported cluster precursor in different ionic liquids were measured and analyzed.

Amorphous aluminum bromide fluoride (ABF)

Different octahedral units form the basis of the structures of the very strong Lewis acids aluminum bromide fluoride (ABF) and aluminum chloride fluoride (ACF) (see picture). A structure model for these phases is established in which the octahedra are linked through μ-bridging fluorine atoms and μ3-bridging X atoms (X = Cl, Br). The bridging of three octahedra by a heavy halogen atom explains the results of NMR and EXAFS analysis.

Characterisation of the tetrahalophosphonium cations PBrnI4 - n+ (0 ≤ n ≤ 4) by 31P MAS NMR, IR and Raman spectroscopy and the crystal structures of PI4+AlCl4-, PI4+AlBr4- and PI4+GaI4-

The novel tetrahalophosphonium salts PBr4+AsF6-, PI4+AlCl4- and PI4+EBr4- (E = Al, Ga) have been synthesised. A variety of solid complexes containing PBr4+ (e.g. PBr4+AsF6-, PBr4+AlBr4- PBr4+GaBr4-), PI4+ (e.g. PI4+AlCl4-, PI4+AlBr4-, PI4+GaBr4-) or the mixed species PBrnI4 - n+ (0 ≤ n ≤ 4, containing AlBr4-, GaBr4-, AsF6- or SbF6-) have been studied by solid-state 31P MAS NMR and vibrational spectroscopy. The influence of the counter-ion on the chemical shift and the vibrational frequencies are discussed. The crystal structures of PI4+AlCl4-, PI4+AlBr4- and PI4+GaI4- are reported. Evidence for the existence of the hitherto unknown mixed bromoiodophosphonium cations PBr3I+, PBr2I2+ and PBrI3+ has been confirmed by spin-orbit corrected density functional calculations of isotropic 31P chemical shifts for PBrnI4 - n+.

The formation of HAlX2 (X = Cl, Br) in the thermolysis of intramolecularly coordinated alanes Me2N(CH2)3AlX2: A matrix isolation study

High-vacuum thermolyses of the intramolecularly coordinated alanes Me2N(CH2)3AlX2 with X = Cl, Br (1, 2) were investigated with matrix isolation techniques. Among the products, which were identified with IR spectroscopy, ab initio calculations, and known literature data, are monomeric HAlCl2 and HAlBr2. The experimental vibrational frequencies of these hydrides matches well the calculated harmonic frequencies at the MP2(fc)/6-311G+(2d, p) and B3LYP/6-311G+(2d, p) level of theory. Beside the monomeric HAlX2, the argon matrices of the thermolysis experiments contained CH4, HCN, H2C=CH2, H2C=NMe, [H2CCHCH2]?, H2C=CHCH3, and AlXn (n = 1-3; X = Cl or Br).

The Preparation and Characterisation by Raman Spectroscopy of AsBr4+AsF6- containing the Tetrabromoarsenic (V) Cation

The thermodynamically unstable AsBr4+AsF6- was prepared by the reaction of AsBr3, Br2, and AsF5 at low temperatures, and characterised by Raman spectroscopy.

Sinthesis and High-Pressure Behaviour of Quaternary Chalcogenide Halides M2M'X3Y (M = Zn, Cd; M' = Al, Ga, In; X = Se, Te; Y = Cl, Br, I)

Quaternary chalcogenide halides M2M'X3Y (M = Zn, Cd; M' = Al, Ga, In; X = Se, Te; Y = Cl, Br, I) can be synthesized by heating stoichiometric amounts of the binary components MX, MY2, and M'2X3 in evacuated sealed quartz ampoules.In the case of aluminium and gallium compounds, a mixture of the M' and X elements rather than the binary compounds has been used.The products are typical tetrahedral compounds, crystallizing with either the defect wurtzite-type or the defect zinc-blende-type structure.At 25 kbar, and 1400 deg C, Cd2InSe3Cl, Cd2InSe3Br, and Cd2InSe3I transform from the defect wurtzite-type structure to quenchable high-pressure phases with defect NaCl-type structure.The retransformation to the ambient-pressure phases proceeds via intermediates having the defect zinc-blende-type structure.Some aspects of the apparent nonstoichiometry in the high-pressure phases are discussed. - Keywords: Quaternary Chalcogenide Halides, Synthesis, Crystal Structure, High-Pressure Reactions