13499-05-3

Basic information

• Product Name: HAFNIUM CHLORIDE
• Synonyms: HAFNIUM(IV) CHLORIDE;HAFNIUM CHLORIDE;HAFNIUM TETRACHLORIDE;(beta-4)-hafniumchloride(hfcl4;Hafnium chloride (HfCl4), (T-4)-;HfCl4;HAFNIUM CHLORIDE, SUBLIMED, 99.9%;HAFNIUM (IV) CHLORIDE ANHYDROUS 98+% (1-3% ZR)
• CAS NO: 13499-05-3
• Molecular Formula: Cl₄Hf
• Molecular Weight: 320.3
• EINECS: 236-826-5
• Product Categories: straight chain compounds;Crystal Grade Inorganics;HafniumMetal and Ceramic Science;Hafnium Salts;Metal and Ceramic Science;Salts;metal halide
• Mol File: 13499-05-3.mol
• Article Data: 3

Chemical Properties

• Melting Point: 319 °C
• Boiling Point: 315.47°C (estimate)
• Appearance: White/Powder
• Density: 1.89 g/cm3
• Vapor Pressure: 1 mm Hg ( 190 °C)
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: Soluble in methanol and acetone.
• Water Solubility: Soluble in water, methanol and acetone.
• Sensitive: Moisture Sensitive
• Merck: 14,4588
• CAS DataBase Reference: HAFNIUM CHLORIDE(CAS DataBase Reference)
• NIST Chemistry Reference: HAFNIUM CHLORIDE(13499-05-3)
• EPA Substance Registry System: HAFNIUM CHLORIDE(13499-05-3)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3260 8/PG 2
• WGK Germany: 3
• F: 9-21
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 13499-05-3(Hazardous Substances Data)

Usage

Chemical Properties

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Physical properties

White monoclinic crystal; sublimes at 317°C; melts at 432°C at 33 atm (triple point); critical temperature 452.5°C; critical pressure 53.49 atm; critical volume 314 cm3/mol; Soluble in methanol, acetone, reacts strongly with water, highly hygroscopic, hydrolyzes in water.

Uses

Different sources of media describe the Uses of 13499-05-3 differently. You can refer to the following data:
1. Hafnium tetrachloride is an important intermediate in production of hafnium metal. It also is used to prepare many hafnium compounds.
2. Hafnium chloride tetrahydrofuran complex is an efficient catalyst for the Diels-Alder cycloadditions, Ziegler-Natta polymerization of alkenes. It is used as control rods in nuclear reactors and in manufacture of light bulb filaments.
3. Hafnium (IV) chloride can be used to catalyze the direct ester condensation of carboxylic acids with alcohols effectively.

Preparation

Hafnium tetrachloride can be prepared (i) by chlorination of hafnium dioxide in the presence of carbon: HfO2 + 2Cl2 + C → HfCl4 + 2CO It also may be prepared by several other methods, such as (ii) reaction of carbon tetrachloride with hafnium dioxide above 450°C; (iii) heating a mixture of hafnium dioxide and carbon above 700°C; and (iv) reaction of chlorine with hafnium at elevated temperatures.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/4ClH.Hf/h4*1H;/p-4

Synthetic route

(cyclopentadienyl)2hafnium dichloride → (η-cyclopentadienyl)hafnium trichloride + hafnium tetrachloride (13499-05-3)

Conditions	Yield
With CCl4; Cl2 Slow introduction of Cl2 (dried over H2SO4) through a gas inlet tube ending above the surface of stirred suspn. of HfCp2Cl2 and dry CCl4 (Ar, 20-23°C, ca. 30 min), occasional cooling of mixt. using ice/water bath.; Removal of Cl2 excess from mixt. with Ar, recovering of resulting materials by filtn. and washing (CCl4, CHCl3, petroleum ether), elem. anal.;	A 55% B n/a

2K(1+)*HfCl6(2-)=K2HfCl6 → hafnium tetrachloride (13499-05-3)

Conditions	Yield
In neat (no solvent) K2HfCl6 was decomposed at just below 500°C;

hafnium + chlorine (7782-50-5) → hafnium tetrachloride (13499-05-3)

Conditions	Yield
In neat (no solvent) sealing of Hf in vac. system, admitting of Cl2 (p(Cl2) = 200 mm), heating;

hafnium(IV) oxide + thionyl chloride (7719-09-7) → hafnium tetrachloride (13499-05-3)

Conditions	Yield
In neat (no solvent, gas phase) thermal-sublimation column, Ar as carrier gas for SOCl2, heating (850°C, 20 min); drying the products over P2O5, elem. anal., product ratio depending on deposition temp.;

disulfur dichloride (10025-67-9) + hafnium(IV) oxide + pyrographite (7440-44-0) → hafnium tetrachloride (13499-05-3)

Conditions	Yield
1200 °C;;
1200 °C;;

tetrachloromethane (56-23-5) + hafnium(IV) oxide → phosgene (75-44-5) + 1,1,2,2-tetrachloroethylene (127-18-4) + carbon dioxide (124-38-9) + chlorine (7782-50-5) + hafnium tetrachloride (13499-05-3)

Conditions	Yield
In neat (no solvent) Kinetics; byproducts: O2; reaction bagins at 540K; mechanism discussed;;
In neat (no solvent) Kinetics; byproducts: O2; reaction bagins at 540K; mechanism discussed;;

hafnium carbide + chlorine (7782-50-5) → hafnium tetrachloride (13499-05-3)

hafnium(IV) oxide + thionyl chloride (7719-09-7) → hafnium oxychloride + hafnium tetrachloride (13499-05-3)

Conditions	Yield
With O2 In neat (no solvent, gas phase) thermal-sublimation column, dried O2-Ar mixture as carrier gas for SOCl2 (pressure: 13 kPa), heating (350 - 375°C, 15 - 120 min); drying the products over P2O5, elem. anal., product ratio depending on deposition temp., not separated;

trifluorormethanesulfonic acid (1493-13-6) + hafnium tetrachloride (13499-05-3) → hafnium tetrakis(trifluoromethanesulfonate)

Conditions	Yield
In not given Ar atmosphere; addn. of acid to Hf-salt, heating (50°C, 68 h); excess of acid removal, washing (petroleum ether), drying (0.5 mm Hg, 100°C, 8 h); elem. anal.;	100%

SiMe2[NC(Ph)NH(tBu)]2 + hafnium tetrachloride (13499-05-3) + toluene (108-88-3) → SiMe2[NC(Ph)NH(tBu)]2HfCl4·(C7H8)

Conditions	Yield
In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Schlenk technique;	100%

C22H32Si(2-)*2Li(1+) + hafnium tetrachloride (13499-05-3) → Me2Si(Cp)(hexenylCp)HfCl2

Conditions	Yield
In diethyl ether at -25 - 20℃; Inert atmosphere; Glovebox;	99.3%

silver trifluoromethanesulfonate (2923-28-6) + hafnium tetrachloride (13499-05-3) + silver nitrate → Hf(H2O)7(NO3)(3+)*3CF3SO3(1-)=[Hf(H2O)7(NO3)](CF3SO3)3 + silver(I) chloride

Conditions	Yield
In water Ag-salts soln. addn. to lanthanide chloride soln., slurry allowing to settle for 1 h, filtration, filtrate vac. concn.; elem. anal.;	A 99% B 96%

pentamethylcyclopentadienyltrimethylsilane (136990-69-7) + hafnium tetrachloride (13499-05-3) → chloro-trimethyl-silane (75-77-4) + pentamethylcyclopentadienylhafnium trichloride (75181-08-7)

Conditions	Yield
In n-heptane Addn. of C5(CH3)5Si(CH3)3 to suspension of HfCl4 in heptane (N2), slowly warming (60 °C), stirring (4 h), cooling.; Filtration, washed (hexane), dried (vacuum), elem. anal.;	A n/a B 99%

selenium (7782-49-2) + selenium tetrachloride (10026-03-6) + hafnium tetrachloride (13499-05-3) → cyclo-tetraselenium(2+) hexachlorohafnate(2-) (166822-46-4)

Conditions	Yield
In neat (no solvent) (argon); evacuated sealed glass ampoule (furnace with temperature gradient 135 to 120°C, 2 d);	99%

hafnium tetrachloride (13499-05-3) + 1,3-diisopropyl-1H-imidazol-3-ium chloride → [1,3-diisopropylimidazolium][(1,3-diisopropylimidazol-2-ylidene)HfCl5]

Conditions	Yield
With benzylpotassium In further solvent(s) in an NMR tube, 2 equiv. of N-comp. and 1-1 equiv. of BzK and HfCl4, resp., were stirred in C6D5Br at ambient temp. for 1 h, under Ar;	99%

tellurium + tellurium tetrachloride (10026-07-0) + hafnium tetrachloride (13499-05-3) → cyclo-tetratellurium(2+) hexachlorohafnate(2-) (166822-47-5)

Conditions	Yield
In neat (no solvent) (argon); evacuated sealed glass ampoule (furnace with temperature gradient 215 to 195°C, 2 weeks);	99%

4,4'-bis(P-((S,S)-[2,6-bis(4'-isopropyl-2'-oxazolinyl)phenyl]gold(I))(diphenylphosphino))biphenyl*(benzene) + hafnium tetrachloride (13499-05-3) + benzene (71-43-2) → 4,4'-bis[P-(chlorogold(I))diphenylphosphino]biphenyl (528522-58-9) + (S,S)-[2,6-bis(4'-isopropyl-2'-oxazolinyl)phenyl]hafnium(IV) trichloride dimer*(benzene)

Conditions	Yield
In tetrahydrofuran under N2; soln. of Au complex in THF added to solid HfCl4; stirred at room temp. for 40 h; solvent evapd. in vac.; benzene added; stirred (room temp., 50 h); centrifuged; decanted; ppt. flushed with hot benzene; centrifuged; combined benzene extracts concd. in vac.; crystd. from benzene-hexane; elem. anal.;	A 99% B 83%

1,4-dithiabutanediyl-2,2'-bis(6-tert-butyl-4-methylphenol) + hafnium tetrachloride (13499-05-3) → dichloro{1,4-dithiabutanediyl-2,2'-bis(6-tert-butyl-4-methylphenoxy)}hafnium

Conditions	Yield
In toluene at -20 - 20℃; for 2.58333h;	98%

2-(benzothiazol-2-yl)phenol (3411-95-8) + hafnium tetrachloride (13499-05-3) → tetrakis(2-(2-hydroxyphenyl)benzothiazole)hafnium (1210945-34-8)

Conditions	Yield
With piperidine In ethanol at 20℃; Inert atmosphere; Reflux;	98%

methylmagnesium bromide (75-16-1) + hafnium tetrachloride (13499-05-3) + 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene → (N-(2,6-diisopropylphenyl)-N-(3-(2,6-diisopropylphenyl)imino-2-methylbutan-2-yl)amino)-trimethylhafnium

Conditions	Yield
Stage #1: hafnium tetrachloride; 1,4-bis(2,6-diisopropylphenyl)-2,3-dimethyl-1,4-diazabuta-1,3-diene In toluene at 23℃; for 1h; Inert atmosphere; Stage #2: methylmagnesium bromide In diethyl ether; toluene at 23 - 40℃; for 2.25h; Inert atmosphere;	98%

1,4-bis(p-carboxyphenyl-ethynyl)-2,3-difluorobenzene + water (7732-18-5) + hafnium tetrachloride (13499-05-3) → [Hf6O4(OH)4(2,3-difluoro-C6H2-1,4-(C≡C-C6H4COO)2)6]n

Conditions	Yield
With hydrogenchloride; L-proline In N,N-dimethyl-formamide at 120℃; for 24h; Reagent/catalyst;	98%

2-tert-butyl-6-[2-[3-[2-(3-tert-butyl-2-hydroxy-5-methylphenyl)phenoxy]propoxy]phenyl]-4-methylphenol + methylmagnesium bromide (75-16-1) + hafnium tetrachloride (13499-05-3) → C39H48HfO4

Conditions	Yield
Stage #1: methylmagnesium bromide; hafnium tetrachloride In diethyl ether; toluene at -35℃; for 0.0833333h; Glovebox; Inert atmosphere; Stage #2: 2-tert-butyl-6-[2-[3-[2-(3-tert-butyl-2-hydroxy-5-methylphenyl)phenoxy]propoxy]phenyl]-4-methylphenol In diethyl ether; toluene at -35 - 20℃; for 1h; Glovebox; Inert atmosphere;	98%

tetrakis(3,5-di-tert-butylpyrazolato)hafnium(IV) + hafnium tetrachloride (13499-05-3) → chlorotris(3,5-di-tert-butylpyrazolato)hafnium(IV) (223480-46-4)

Conditions	Yield
In dichloromethane Ar-atmosphere; stoich. amts., stirring at room temp. for 16 h; removal of volatiles (reduced pressure), extn. into hexane, filtration (Celite), removal of volatiles (reduced pressure); elem. anal.;	97%

hafnium tetrachloride (13499-05-3) + 1-methyl-2-(trimethylstannyl)-1,2-dihydroborinine (186891-73-6) → trichloro(1-methylboratabenzene)hafnium (193680-95-4)

Conditions	Yield
In hexane N2-atmosphere; stirring (20°C, 1 h); washing (hexane), drying (vac.);	97%

lithium dimethylsilylbis(trimethylsilylmethylcyclopentadienide) + hafnium tetrachloride (13499-05-3) → dimethylsilylbis((trimethylsilyl)methylcyclopentadienide)hafnium dichloride

Conditions	Yield
In diethyl ether at -25 - 20℃;	97%

C26H29N2P + methylmagnesium bromide (75-16-1) + hafnium tetrachloride (13499-05-3) → C48H54HfN4P2

Conditions	Yield
Stage #1: methylmagnesium bromide; hafnium tetrachloride In diethyl ether; toluene at 23℃; for 0.00277778h; Inert atmosphere; Stage #2: C26H29N2P In diethyl ether; toluene for 2h;	97%

formic acid (64-18-6) + benzene-1,3,5-tricarboxylic acid (554-95-0) + water (7732-18-5) + hafnium tetrachloride (13499-05-3) → Hf-MOF-808

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	97%

2,2-bis(cyclopentadienyl)propane, dilitium salt + hafnium tetrachloride (13499-05-3) → HfCl2((C5H4)2C(CH3)2) (163657-15-6)

Conditions	Yield
With trimethyltin(IV)chloride In diethyl ether; toluene inert atmosphere; addn. of Me3SnCl to Li-salt in Et2O at -40°C, warming to room temp., evapn., addn. of ZrCl4 suspn. in toluene, stirring(80°C, 4 h); evapn. (80-90°C, 1 torr), recrystn. or washing;	96%

hafnium tetrachloride (13499-05-3) + trimethylsilylmethyllithium (1822-00-0) → tetrakis(trimethylsilylmethyl)hafnium (40334-04-1)

Conditions	Yield
In diethyl ether; hexane distillation at about 50 °C and 10E-3 Torr;;	96%
In diethyl ether; hexane distillation at about 50 °C and 10E-3 Torr;;	96%

hafnium tetrachloride (13499-05-3) + trityl chloride (76-83-5) → bis(triphenylmethylium)di-μ-chloro-bis{tetrachlorohafnate(IV)}

Conditions	Yield
In dichloromethane Under Ar, treatment of a suspn. of HfCl4 with Ph3CCl, immediate dissolution and formation of a yellow-orange colour is observed.; Filtn., addn. of n-pentane to form two layers, after 15 h large orange crystals are present, filtn., washing (n-pentane), drying in vac., elem. anal.;	96%

C45H62N2OSi2(2-)*2Li(1+) + hafnium tetrachloride (13499-05-3) → C45H62Cl2HfN2OSi2 (1191275-86-1)

Conditions	Yield
In toluene at 80 - 100℃; for 75.5h;	96%

2-(2-Hydroxyphenyl)benzoxazole (835-64-3) + hafnium tetrachloride (13499-05-3) → tetrakis(2-(2-hydroxyphenyl)benzoxazole)hafnium (1210945-33-7)

Conditions	Yield
With piperidine In ethanol at 20℃; Inert atmosphere; Reflux;	95%
Stage #1: 2-(2-Hydroxyphenyl)benzoxazole With potassium hydride In tetrahydrofuran at -30℃; Stage #2: hafnium tetrachloride	66%

4,4′-ethynylenedibenzoic acid (16819-43-5) + water (7732-18-5) + hafnium tetrachloride (13499-05-3) → [Hf6O4(OH)4(4,4′-ethynylenedibenzoate)6]n

Conditions	Yield
With hydrogenchloride; L-proline In N,N-dimethyl-formamide at 120℃; for 24h; Sealed tube;	95%

formic acid (64-18-6) + water (7732-18-5) + hafnium tetrachloride (13499-05-3) + 4,4′,4′′-[benzene-1,3,5-triyltris(ethyne-2,1-diyl)]tribenzoic acid (205383-17-1) → [Hf6O4(OH)8(HCO2)2(4,4′,4″-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate)2(H2O)x]n

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 72h;	95%

lithium diphenylsilyl(tetramethylcyclopentadienide)((trimethylsilyl)methylcyclopentadienide) + hafnium tetrachloride (13499-05-3) → diphenylsilyl(tetramethylcyclopentadienide)((trimethylsilyl)methylcyclopentadienide)hafnium dichloride

Conditions	Yield
In diethyl ether at -25 - 20℃;	95%

formic acid (64-18-6) + 1,3,5-tri(2'-carboxyphenyl)benzene (955050-88-1) + water (7732-18-5) + hafnium tetrachloride (13499-05-3) → Hf6(μ3-O)4(μ3-OH)4(HCO2)6(benzene-1,3,5-tribenzoate)2

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	95%

formic acid (64-18-6) + 4’-(4-benzoate)-(2,2’,2’’-terpyridine)-5,5’’-dicarboxylate + water (7732-18-5) + hafnium tetrachloride (13499-05-3) → 2C24H12N3O6(3-)*6CHO2(1-)*4HO(1-)*6Hf(4+)*4O(2-)

Conditions	Yield
In N,N-dimethyl-formamide at 120℃; for 48h;	95%
In N,N-dimethyl-formamide at 120℃; for 48h;	85%

C17H24Si(2-)*2Li(1+) + hafnium tetrachloride (13499-05-3) → Me(H)Si(n-PrCp)2HfCl2, Cp=cyclopentadienyl

Conditions	Yield
In diethyl ether at -25 - 20℃; for 48h; Inert atmosphere; Glovebox;	94.1%

Upstream product

• 7782-50-5 chlorine 
• 7719-09-7 thionyl chloride 
• 10025-67-9 disulfur dichloride 
• 7440-44-0 pyrographite 
• 56-23-5 tetrachloromethane 
• 7647-01-0 hydrogenchloride 

Downstream Products

• 97-88-1 2-methyl-butyl acrylate 
• 7647-01-0 hydrogenchloride 
• 12027-05-3 hafnium hydroxide 
• 133158-34-6 {1.2-bis(diphenylphosphino)propane-P,P'}tetrachlorohafnium(IV) 
• 75-77-4 chloro-trimethyl-silane 
• 122448-35-5 {C₆H₅C(NSi(CH₃)3)2HfCl₃}*{C₆H₅C(NSi(CH₃)3)(N(Si(CH₃)3)2)} 
• 13777-22-5 hafnium tetrabromide 
• 12116-66-4 bis(cyclopentadienyl)hafnium dichloride 
• 10035-10-6 hydrogen bromide 
• 39292-59-6 C₈H₈HfC₈H₈ 
• 40334-04-1 tetrakis(trimethylsilylmethyl)hafnium 

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