13470-13-8

Usage

Uses

Used in Electronics Industry:
Tungsten tetrachloride is used as a precursor reactant for the preparation of highly conductive tungsten diselenide nanosheets. These nanosheets are essential components in the development of advanced electronic devices and materials due to their unique electrical and optical properties.
Used in Chemical Synthesis:
Tungsten tetrachloride serves as an important intermediate in the synthesis of various tungsten-containing compounds. Its ability to react with a wide range of chemicals makes it a valuable building block for the production of complex molecules and materials.
Used in Metallurgical Processes:
In the metallurgical industry, tungsten tetrachloride is utilized in the production of tungsten metal and its alloys. The compound's reactivity and stability make it suitable for use in the reduction processes required to obtain pure tungsten or tungsten-based alloys.
Used in Catalysts:
Tungsten tetrachloride is employed as a catalyst or catalyst precursor in various chemical reactions. Its ability to facilitate specific transformations makes it a valuable tool in the synthesis of pharmaceuticals, polymers, and other specialty chemicals.
Used in Research and Development:
Due to its unique chemical properties, tungsten tetrachloride is often used in research and development settings to study the fundamental aspects of chemical reactions and to develop new materials with novel properties. Its sensitivity to moisture and tendency to decompose upon heating make it an interesting subject for scientific investigation.

InChI:InChI=1/4ClH.W/h4*1H;/q;;;;+4/p-4

Synthetic route

hydrogenchloride (7647-01-0) + tungstic acid + zinc (7440-66-6) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
strong HCl;	100%
strong HCl;	100%

tungsten(VI) chloride (13283-01-7) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
With Sn In 1,2-dichloro-ethane byproducts: SnCl4; absence of air and moisture; stirring with Sn-powder at room temp. for 17 h, then at 80-90°C for 2 d; centrifugation, washing (CH2Cl2), drying (vac., room temp.); elem. anal.;	98%
With Sb In neat (no solvent) byproducts: SbCl3, WOCl4, WCl5; absence of air and moisture; sealed evacuated glass tube, 75-80°C(12 h), 105°C (12 h), 130°C (12 h); distn. off of byproducts (130°C, 1d; then 160°C, 1 d; then215°C, 1 d); elem. anal.;	97%
With red phosphorus In neat (no solvent) byproducts: PCl3, WOCl4, WCl5; absence of air and moisture; sealed evacuated glass tube, slow heating to 200°C (over 12 h), then to 300°C (over further 12 h); sublimation off of byproducts (230-240°C, 1 d, trap at liquid N2-temp.; further byproduct: POCl3); elem. anal.;	94%

phosphorous + tungsten(VI) chloride (13283-01-7) → W4PCl11 + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) byproducts: PCl3; WCl6 and red P (1:1.34) mixed (Ar), sealed (vac.) in silica tube, heatedat 500°C for 24 h; sublimated, XRD;	A 95% B 5%

tungsten(VI) chloride (13283-01-7) + tungsten (7440-33-7) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In 1,2-dichloro-ethane at 20℃; for 17h;	93%

hydrogenchloride (7647-01-0) + aluminium trichloride (7446-70-0) + tungsten(VI) chloride (13283-01-7) + aluminium (7429-90-5) + sodium chloride (7647-14-5) → W6Cl8(4+)*4Cl(1-)*7H2O=[W6Cl8]Cl4*7H2O + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent, solid phase) other Radiation; sealing WCl6, Al, AlCl3 and NaCl and Mo into SiO2 ampoule (1E-2 Torr N2), microwave oven (200 W, 60 min, cooling to room temp., further irradiation at 200 W for 60 min), opening, dissoln. in hot concd. HCl; filtration (Celite), crystn. on cooling, washing (cold. concd. HCl, Et2O), drying (overnight); elem. anal.;	A 48% B n/a

tungsten(VI) chloride (13283-01-7) + tungsten (7440-33-7) → tungsten(VI) oxychloride (13520-78-0, 160797-03-5) + tungsten dichloride + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
reaction of WCl6 with W at 270-750°C for 14 h under a vacuum; removal of WCl4 and WOCl4 byproducts by sublimation, intermediate (H3O)2W6Cl14*6H2O obtained after recrystn. from boiling HCl and cooling to -10°C; intermediate heated at 450°C under a dynamic vacuum;	A n/a B 25% C n/a

tetrachloromethane (56-23-5) + tungsten(IV) oxide → tungsten(VI) oxychloride + tungsten(VI) chloride (13283-01-7) + tungsten(IV) chloride (13470-13-8) + tungsten dioxydichloride (13520-76-8)

Conditions	Yield
In neat (no solvent) reaction on heating WO2 with CCl4 to 250°C in a closed tube for 8h;;
In neat (no solvent) reaction on heating WO2 with CCl4 to 250°C in a closed tube for 8h;;

tungsten(VI) chloride (13283-01-7) → chlorine (7782-50-5) + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In gas Kinetics; Irradiation (UV/VIS); stationary photolysis in a glass cell; flash photolysis in a sealed quartz cell; vac. distn.;

hydrogen (1333-74-0) + tungsten(VI) chloride (13283-01-7) → tungsten(V) chloride (13470-14-9) + chlorine (7782-50-5) + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In gas Kinetics; byproducts: HCl; Irradiation (UV/VIS); flash photolysis in a sealed quartz cell at 388 K and 403 K; stationaryphotolysis in a sealed glass cell at 140°C; vac. distn.;

tungsten(VI) chloride (13283-01-7) + aluminium (7429-90-5) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) sealed ampoule (270-280 °C, 15 h), molar ratio WCl6:Al = 1:1.5;
In neat (no solvent, solid phase) reaction in glass ampules at 400°C;

tungsten (7440-33-7) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
With Cl2 Kinetics; pulsed chlorine molecular beam reaction with W (300-1350°C, modulated beam-mass spectrometric equipment, base pressure 1E-9 Torr); MS; WCl4 is main product up to ca. 1000°C;
With Cl Kinetics; pulsed atomic chlorine beam (generated by RF plasma discharge) reaction with W (300-1350°C, modulated beam-mass spectrometric equipment, base pressure 1E-9 Torr); MS; WCl4 is main product up to ca. 1000°C;

tungsten oxychloride + tungsten(VI) chloride (13283-01-7) → tungsten(VI) oxychloride + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) equimolar amts.; sealed evacuated ampoule, 200-250°C (2 h; condensation of WOCl4 in cold part), then heating to 360°C; elem. anal.;
stoich. mixt. heating (evac. sealed two-section ampoule, 200-250°C for 2 h, WOCl4 crystn. in cold part of ampoule), temp. raising to 360°C; thermogravimetric and differential thermal anal.;

tetrachloromethane (56-23-5) + tungsten(IV) oxide → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
heating at 280°C in a closed tube by melting;
heating at 280°C in a closed tube by melting;

tungsten(VI) chloride (13283-01-7) → tungsten(V) chloride (13470-14-9) + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
With hydrogen redn. above 350°C; heating in H2 or CO2-stream, distn.;
With hydrogen redn. above 350°C; heating in H2 or CO2-stream, distn.;

tungsten hexacarbonyl (14040-11-0) + tungsten(VI) chloride (13283-01-7) → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In chlorobenzene byproducts: CO; under N2 solvent was added to mixt. of educts; stirring at reflux ca 12h; filtration, washing with PhCl, rinsing with CH2Cl2 or pentane, drying;	>99
In chlorobenzene W(CO)6 was refluxed with WCl6 in chlorobenzene under Ar;

tungsten(IV) oxide + tungsten(VI) chloride (13283-01-7) → tungsten(VI) oxychloride + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) 2 equiv. of WCl6; sealed evacuated ampoule, 200-250°C (2 h; condensation of WOCl4 in cold part), then heating to 360°C; elem. anal.;
stoich. mixt. heating (evac. sealed two-section ampoule, 200-250°C for 2 h, WOCl4 crystn. in cold part of ampoule), temp. raising to 360°C; thermogravimetric and differential thermal anal.;

tungsten(IV) oxide → tungsten(IV) chloride (13470-13-8)

Conditions	Yield
With tetrachloromethane in closed tube at 250°C;
With CCl4 in closed tube at 250°C;

tungsten(IV) oxide → tungsten dioxide dichloride + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
With chlorine
With Cl2

2Cu(2+)*W(4+)*2CN(1-)*2OH(1-)*H2NC2H4NH2*2H2O*4Cl(1-)=Cu2[W(CN)2(OH)2(C2H8N2)(H2O)2]Cl4 → copper(l) cyanide + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) Kinetics; byproducts: H2O, ethylenediamine; sample heating in N2 flow (50 ml/min) at 10 K/min between 30-800°C; TG, DTG, DSC;

zinc nitride + tungsten(VI) chloride (13283-01-7) → W2NCl8 + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent, solid phase) byproducts: ZnCl2, N2; under Ar; WCl6 and Zn3N2 in 3:1 molar ratio carefully mixed; heated at 230°C in evacuated and sealed ampoule; kept at this temp. for 1 week; cooled to 200°C in 40 h and to room temp. in 12 h;

manganese tungstate + chlorine (7782-50-5) → tungsten(V) chloride (13470-14-9) + tungsten(VI) oxychloride + tungsten(VI) chloride (13283-01-7) + tungsten(IV) chloride (13470-13-8)

Conditions	Yield
In neat (no solvent) Kinetics; High Pressure; linear heating rate of 5.3°C/min, Cl2(gas)-Ar(gas) flow = 4 L/h, pressure of Cl2 - 35 kPa, temperature range: 650-850°C; XRD;

manganese tungstate + chlorine (7782-50-5) → tungsten(IV) chloride (13470-13-8) + manganese(ll) chloride

Conditions	Yield
In neat (no solvent) Kinetics; byproducts: O2; reaction in flow of Ar and Cl2, at temperature range 50-950°C;

tungsten(IV) chloride (13470-13-8) + acetonitrile (75-05-8) → trans-WCl4(MeCN)2 (12073-20-0, 223383-17-3, 223393-83-7, 40354-88-9)

Conditions	Yield
In acetonitrile stirring (2 days); solvent removal (vac.);	100%

tungsten(IV) chloride (13470-13-8) + sodium chloride (7647-14-5) → Na3[W3(μ3-Cl)(μ-Cl)3Cl9] + Na(1+)*W3Cl13(1-)=Na[W3Cl13]

Conditions	Yield
In neat (no solvent, solid phase) NaCl:WCl4=3:1, under inert atm., evacuated silica ampoule, heating up to500 °C in 5 h, keeping at this temp. for 48 h; cooling to 300 °C in 72 h, then to room temp. in 2 h;	A 99% B 0%

N-benzyl-N,N,N-triethylammonium chloride (56-37-1) + tungsten(IV) chloride (13470-13-8) → C6H5CH2N(C2H5)3(1+)*WCl6(1-)=C6H5CH2N(C2H5)3WCl6 (215669-98-0) + 2C6H5CH2N(C2H5)3(1+)*W2Cl9(2-)=[C6H5CH2N(C2H5)3]2W2Cl9

Conditions	Yield
In dichloromethane react. for several days at 25°C, filtration, washing (CH2Cl2), drying (vac.), cooling of supenatant and crystn. of WCl6-salt; elem. anal.;	A 37% B 96%

sodium benzoate (532-32-1) + trimethylsilyl iodide (16029-98-4) + tungsten(IV) chloride (13470-13-8) + bis-diphenylphosphinomethane (2071-20-7) → W2(μ-O2CC6H5)2I2(μ-dppm)2 * 1/2 THF * 1/2 hexanes

Conditions	Yield
With Na(HBEt3) In tetrahydrofuran Ar-atmosphere; addn. of NaHBEt3 to mixt. of WCl4 and benzoate at -70°C, warming to room temp., addn. of dppm and Me3SiI, gentle heating for 24 h; washing (hexanes), solvent removal;	94%

tungsten(IV) chloride (13470-13-8) + Dimethyl(phenyl)phosphine (672-66-2) → W2Cl4(P(CH3)2(C6H5))4 (73133-21-8, 147977-45-5)

Conditions	Yield
With sodium amalgam In tetrahydrofuran under N2 sodium amalgam and Me2PPh were added to THF at -30°C followed by WCl4; shaking and warming to room temp. for ca 0.5 h; decantation, filtration through Celite; evapn., extn. with pentane, filtration, evapn., washing with MeCN, drying in vac.; elem. anal.;	90%
With NaB(C2H5)3H In tetrahydrofuran; toluene Ar atmosphere; addn. of soln. of NaBHEt3 in toluene to soln. of WCl4 in THF (-60°C), stirring (20 min), addn. of org. compd., slow warming (room temp., 0.5 h), stirring (12 h, room temp.); removal of solvent (vac.), dissolution in THF, filtration (Celite), pptn. on addn. of hexane, washing (hexane and MeOH), drying (vac.);	76%
With sodium amalgam In tetrahydrofuran 2 equiv of sodium amalgam added to a stirred soln. of WCl4 and PMe2Ph at -20°C, warmed to room temp.; filtered through Celite; elem. anal.;

N-benzyl-N,N,N-triethylammonium chloride (56-37-1) + tungsten(IV) chloride (13470-13-8) → (BnEt3N)[W2(μ-Cl)3Cl6] (215669-96-8)

Conditions	Yield
In dichloromethane stirring 1 day, filtration, evapn., crystn.; elem. anal.;	90%

tetrabutyl-ammonium chloride (1112-67-0) + tungsten(IV) chloride (13470-13-8) → (n-Bu4N)3[W2(μ-Cl)3Cl6]

Conditions	Yield
With sodium amalgam In toluene under inert atm. to mixt. WCl4 and Bu4NCl in toluene Na/Hg was added andstirred for 24 h; soln. was filtered through Celite and evapd. in vacuo, residue was dissolved in MeCN, filtered, concd. and cooled at -20°C, ppt. was filtered, recrystd. from MeCN and dried in vacuo; elem. anal.;	90%

bis(tert-butyl) diselenide (34172-61-7) + tungsten(IV) chloride (13470-13-8) → tungsten(IV) selenide

Conditions	Yield
With n-Dodecylamine at 150 - 225℃; for 6h; Inert atmosphere;	90%

tungsten(IV) chloride (13470-13-8) + diphenyl(methyl)phosphine (1486-28-8) → W2(P(CH3)(C6H5)2)4Cl4 (73133-22-9)

Conditions	Yield
With sodium amalgam In tetrahydrofuran under N2 sodium amalgam and MePPh2 were added to THF at -30°C followed by WCl4; shaking and warming to room temp. for ca 0.5 h; decantation, filtration through Celite; extn. of Celite with CH2Cl2, combining of exts. and filtrate, evapn.; elem. anal.;	88%
With sodium amalgam In tetrahydrofuran 2 equiv of sodium amalgam added to a stirred soln. of WCl4 and PMePh2 at -20°C, warmed to room temp.; filtered through Celite; elem. anal.;

α-W2Cl2(1,2-bis(diphenylphosphino)ethane)2 (73133-24-1, 73470-13-0, 86782-93-6) + tungsten(IV) chloride (13470-13-8) + 1,2-bis-(diphenylphosphino)ethane (1663-45-2) → C52H48Cl6P4W2

Conditions	Yield
With sodium amalgam; THF In tetrahydrofuran stirring a suspension of WCl4 with Na/Hg, -20°C, 30 min; allowing to warm to room temp.; filtration under Ar; extn. of residue with fresh THF; reducing volume of filtrate; addn. of phosphinoethane; refluxing, 15 min; stirring, room temp., 1h; reducing volume; addn. of hexane; pptn.; filtration; washing (ethanol, Et2O); elem. anal.;	87%

tungsten(IV) chloride (13470-13-8) → W2Cl6(OC4H8)4

Conditions	Yield
With tetrahydrofuran; sodium amalgam In tetrahydrofuran under N2 WCl4 was added to THF contg. sodium amalgam; stirring for 1 h; filtration through Celite; evapn., trituration with pentane, prepd. powder was crystd. from THF/pentane; elem. anal.;	86%
With tetrahydrofuran; sodium amalgam In tetrahydrofuran 1 equiv of sodium amalgam added to a stirred soln. of WCl4; pentane added;

sulfure de pentamethylene (1613-51-0) + sodium amalgam + tungsten(IV) chloride (13470-13-8) → Cl3W(μ-pentamethylene sulfide)3WCl3 (216670-48-3) + [Na][Cl3W(μ-pentamethylene sulfide)2(μ-Cl)WCl3] (216670-71-2)

Conditions	Yield
In toluene inert atmosphere; refluxing for 45 min; cooling, pptn. on Et2O addn., extn. into CH2Cl2, then into Me2CO, repeated recrystn.; elem. anal.;	A 86% B 9.5%
In neat (no solvent) inert atmosphere; refluxing;

tetraphenyl phosphonium chloride (2001-45-8) + tungsten(IV) chloride (13470-13-8) → (Ph4P)3[W2(μ-Cl)3Cl6]

Conditions	Yield
With sodium amalgam In toluene under inert atm. to mixt. WCl4 and Ph4PCl in toluene Na/Hg was added andstirred for 24 h; soln. was filtered through Celite and evapd. in vacuo, residue was dissolved in MeCN, filtered, concd. and cooled at -20°C, ppt. was filtered, recrystd. from MeCN and dried in vacuo; elem. anal.;	86%

2,4,6-triisopropylbenzoate sodium (1115265-86-5) + tungsten(IV) chloride (13470-13-8) → tetrakis(2,4,6-triisopropylbenzoato)ditungsten

Conditions	Yield
With Na/Hg In tetrahydrofuran (N2); addn. of sodium benzoate deriv. to sodium amalgam, addn. of suspn.of tungsten compd. in dry THF at 0°C, stirring for 30 min at 0.d egree.C, warming to room temp., stirring overnight; filtration through celite, concg., keeping in cold overnight, filtration, recrystn. (THF), elem. anal.;	86%

tributylphosphine (998-40-3) + tungsten(IV) chloride (13470-13-8) → W2Cl4(P(n-Bu)3)4 (73133-23-0)

Conditions	Yield
With sodium amalgam In tetrahydrofuran under N2 sodium amalgam and Bu3P were added to THF at -30°C followed by WCl4; shaking and warming to room temp. for ca 0.5 h; decantation, filtration through Celite; evapn., extn. with pentane, filtration, evapn., washing with MeCN, drying in vac.; elem. anal.;	85%
With sodium amalgam In tetrahydrofuran 2 equiv of sodium amalgam added to a stirred soln. of WCl4 and PBu3 at -20°C, warmed to room temp.; filtered through Celite; elem. anal.;

sodium benzoate (532-32-1) + tungsten(IV) chloride (13470-13-8) → ditungsten(II) tetrabenzoate (110173-58-5)

Conditions	Yield
With NaBEt3H In tetrahydrofuran Ar-atmosphere; addn. of NaBEt3H to suspn. of WCl4 and benzoate at -60°C, slow warming to room temp.; filtration (Celite), washing (hexanes);	85%
With sodium In not given under N2 or Ar;

depe (6411-21-8) + tungsten(IV) chloride (13470-13-8) → α-W2Cl4(1,2-bis(diethylphosphino)ethane)2 (205590-12-1) + [WOCl(1,2-bis(diethylphosphino)ethane)2]2[(WOCl4(OP(C2H5)2CH2))2]

Conditions	Yield
With NaBEt3H In tetrahydrofuran Ar-atmosphere; slow addn. of excess of NaBEt3H to WCl4 at -60°C, addn. of excess of ligand at -20°C, warming to room temp., stirring overnight; pptn. on hexanes addn., filtration, washing (hexanes), drying (vac.);	A 84.7% B n/a
With NaBEt3H; PMePh2 In tetrahydrofuran Ar-atmosphere; slow addn. of 2 equiv. of NaBEt3H to WCl4 at 0°C, addn. of 2 equiv. PMePh2, warming to room temp., addn. of excess of ligand, stirring (room temp., 2 h); pptn. on hexanes addn., filtration, washing (hexanes), drying (vac.);	A 70.6% B n/a

Bis(diphenylphosphanyl)amine (2960-37-4) + tungsten(IV) chloride (13470-13-8) → W2Cl4(μ-bis(diphenylphosphino)amine)2 (264202-30-4)

Conditions	Yield
With NaBH(CH2CH3)3 In tetrahydrofuran under Ar; WCl4 was suspended in THF, cooled to -60°C in EtOH/dry ice bath, NaBEt3H was added, mixt. was warmed to -20°C, soln. wasadded to the amine at room temp.; washed with hexane, remaining solvent was removed under vac.;	81.4%

thiophene (110-01-0) + tungsten(IV) chloride (13470-13-8) → {Cl3W(μ-tetrahydrothiophene)3WCl3} (132935-81-0)

Conditions	Yield
With Na#Hg In thiophene heating to boiling point of tht, stirring for 20 min in a Schlenk tube;; cooling, decantation, washing with ether, extn., recrystn.; elem. anal.;;	81%
With Na#Hg In thiophene stirring at 22°C for 24 h;;	58%

tungsten(IV) chloride (13470-13-8) + acetonitrile (75-05-8) → tetrachlorobis(acetonitrile)tungsten(IV) (223383-17-3, 223393-83-7, 40354-88-9, 12073-20-0)

Conditions	Yield
In acetonitrile absence of air and moisture; stirring at room temp. for 2 d; decantation, washing (MeCN), drying (vac.); elem. anal.;	81%

1,4-Oxathiane (15980-15-1) + sodium amalgam + tungsten(IV) chloride (13470-13-8) → Cl3W(μ-1,4-thioxane)3WCl3 (216670-42-7) + [Na][Cl3W(μ-1,4-thioxane)2(μ-Cl)WCl3] (216670-62-1)

Conditions	Yield
In toluene inert atmosphere; refluxing for 25 min; cooling, pptn. on Et2O addn., extn. into CH2Cl2, then into Me2CO, repeated recrystn.; elem. anal.;	A 15.3% B 81%
In neat (no solvent) inert atmosphere; refluxing;

sodium benzoate (532-32-1) + tungsten(IV) chloride (13470-13-8) → W2(O2CC6H5)4(C4H8O)2 (82752-90-7)

Conditions	Yield
With tetrahydrofuran; sodium amalgam In tetrahydrofuran byproducts: sodium chloride; under Ar atm. WCl4 react. with 2 equiv. 0.4% sodium amalgam in THF at -20°C, 2 equiv. sodium benzoate added to W2Cl4(THF)4 added and stirred for 1/2 h and mixt. warmed to room temp.; soln. filtered through Celite, filtrate chilled to -20°C for 3 days;	80%
With C4H8O; Na#Hg In tetrahydrofuran byproducts: NaCl, Hg; (absence of air); WCl4 treated with 2 equiv of Na#Hg in THF at -20°C, sodium benzoate added, allowed to warm to room temp. with stirringfor 0.5 h; filtered, covered with hexane, crystd. for 3 d - 1 wk;	55%

tert-butylamine (75-64-9) + tungsten(IV) chloride (13470-13-8) → tetrachlorobis(t-butylamido)bis(t-butylamine)ditungsten(II)

Conditions

Yield

With Na/Hg; THF In tetrahydrofuran byproducts: (NH3(C(CH3)3))Cl; (N2); t-BuNH2 (43.6 mmol) added to stirred soln. of W2Cl6(THF)4 formed in situ by redn. of WCl4 (14.52 mmol) with 1 equiv. of Na/Hg (0.4%) in THF; stirring for 14 h; filtration; solvent removed (reduced pressure) from filtrate; residue extd. (hot hexane); filtration; solvent stripped from filtrate to give single crystals; elem. anal.;

78%

lithium dimethylamide (3585-33-9) + tungsten(IV) chloride (13470-13-8) → hexakis(dimethylamido)ditungsten(III) (54935-70-5)

Conditions	Yield
at 0℃; for 2h; Reflux;	77%
With sodium amalgam; THF In tetrahydrofuran byproducts: W(NMe2)6; 1 equiv of 1.0% Na amalgam was slowly (90 min) added to a slurry of WCl4 in THF at 0°C under N2, mixt. was stirred for 3 h at room temp., cooled to 0°C, 3 equiv of LiNMe2 was added slowly (2 h), mixt. was stirred for 12 h at room temp.; filtered through Celite (washed with THF), solvent was removed in vacuo, residue was sublimed at 120°C and 0.0001 Torr; the first isolated fraction (ca. 10%) was occasionally contaminated with small quantities of W(NMe2)6;	75%
In tetrahydrofuran; diethyl ether at 0℃; for 25h; Reflux;

diethyl sulphide (352-93-2) + tungsten(IV) chloride (13470-13-8) → {Cl3W((CH3CH2)2S)3WCl3}*CH2Cl2

Conditions	Yield
With Na#Hg In further solvent(s) solvent: Et2S; stirring for 40 min in a Schlenk tube;; extn. with CH2Cl2, evapn.;;	77%

tungsten(IV) chloride (13470-13-8) + trimethylphosphane (594-09-2) → W2Cl6(P(CH3)3)4

Conditions	Yield
With sodium amalgam In tetrahydrofuran 1 equiv of sodium amalgam added to a stirred soln. of WCl4 and PMe3; NMR;	75%

Upstream product

• 56-23-5 tetrachloromethane 
• 13283-01-7 tungsten(VI) chloride 
• 1333-74-0 hydrogen 
• 7429-90-5 aluminium 
• 7440-33-7 tungsten 
• 7647-01-0 hydrogenchloride 
• 7440-66-6 zinc 
• 14040-11-0 tungsten hexacarbonyl 
• 7446-70-0 aluminium trichloride 
• 7647-14-5 sodium chloride 
• 7782-50-5 chlorine 

Downstream Products

• 7440-33-7 tungsten 
• 122647-65-8 dichloro(5,10,15,20-meso-tetra-p-tolylporphyrinato)tungsten(IV) 
• 106297-42-1 W₂Cl₆(bis(diphenylphosphino)methane)2 
• 113471-51-5 {W₃S₄Cl₃(P(CH₃)2CH₂CH₂P(CH₃)2)3}⁽¹⁺⁾*B(C₆H₅)4^(1-)={W₃S₄Cl₃(P(CH₃)2CH₂CH₂P(CH₃)2)3}{B(C₆H₅)4} 
• 7440-36-0 antimony 
• 13470-14-9 tungsten(V) chloride 
• 13283-01-7 tungsten(VI) chloride 
• 12039-88-2 tungsten silicide 
• 20193-56-0 tungsten(III) chloride 
• 139376-26-4 W₂Cl₆(P(CH₃)2C₆H₅)4 
• 139376-27-5 W₂Cl₆(P(CH₃)2C₆H₅)3 
• 73133-22-9 W₂(P(CH₃)(C₆H₅)2)4Cl₄ 
• 73133-21-8 W₂Cl₄(P(CH₃)2(C₆H₅))4 
• 93110-48-6 tetrakis(2-anilinopyridine)ditungsten(II)*2/3THF 

Relevant academic research and scientific papers

Beyond the conventional number of electrons in M6X12 type metal halide clusters: W6Cl18, (Me4N) 2[W6Cl18], and Cs2[W 6Cl18]

Black octahedral single crystals of W6Cl18 were obtained by reducing WCl4 with graphite in a silica tube at 600°C. The single crystal structure refinement (space group R 3, Z = 3, a = b = 1498.9(1) pm, c = 845.47(5) pm) yielded the W6Cl 18 structure, already reported on the basis of X-ray powder data. (Me4N)2[W6Cl18] and Cs 2[W6Cl18] were obtained from methanolic solutions of W6Cl18 with Me4NCl and CsCl, respectively. The structure of (Me4N)2[W 6Cl18] was refined from X-ray single crystal data (space group P 3ml, Z = 1, a = b = 1079.3(1) pm, c = 857.81(7) pm), and the structure of Cs2[W6Cl18] was refined from X-ray powder data (space group P 3, Z = 1, a = b = 932.10(7) pm, c = 853.02(6) pm). The crystal structure of W6Cl18 contains molecular W6Cl18 units arranged as in a cubic closest packing. The structures of (Me4N)2[W6Cl18] and Cs2[W6Cl18] can be considered as derivatives of the W6Cl18 structure in which 2/3 of the W 6Cl18 molecules are substituted by Me4N + ions and Cs+ ions, respectively. The conventional number of 16 electrons/cluster is exceeded in these compounds, with 18 electrons for W6Cl18 and 20 electrons for (Me4N) 2[W6Cl18] and Cs2[W 6Cl18]. Cs2[W6Cl18] exhibits temperature independent paramagnetic behaviour.

Phosphorus-centered and phosphinidene-capped tungsten chloride clusters

Black crystalline powders of W6PCl17 and W 4(PCl)Cl10 were obtained after reducing WCl6 with red phosphorus at 370 and 500 °C. The crystal structures were determined by single-crystal and powder X-ray

KINETICS OF TUNGSTEN ETCHING BY ATOMIC AND MOLECULAR CHLORINE.

The reactions of atomic and molecular chlorine with tungsten were studied by modulated beam-mass spectrometric methods over the temperature range 300-1350 K. The atomic beam was generated by an rf plasma discharge. With both atomic and molecualr beams, the main reaction product up to about 1000 K was WCl//4. The reaction probability with atomic chlorine was a factor of approximately ten higher than that obtained with molecular chlorine. The reaction was nonlinear with respect to Cl//2 intensity at low beam fluxes but approached linearity at high beam intensities. Above 1000 K the main reaction product was atomic chlorine. Its reaction probability increased rapidly with temperature; at 1300 K nearly complete dissociation of Cl//2 was observed. A kinetic model based on the Eley-Rideal mechanism was proposed and compared with the data. AA. 20 Refs.

Synthesis of Alkyne Metathesis Catalysts from Tris(dimethylamido)tungsten Precursors

Benzylidyne tungsten systems bearing a combination of alkoxide and amide ligands were readily obtained by partial alcoholysis of amido-supported tungsten complexes. Benzylidyne tris(dimethylamido)tungsten was treated with fluorinated alcohols Me2(CF3)COH, Me(CF3)2COH, and (CF3)3COH, and also with silanols (tBuO)3SiOH, and Ph3SiOH, all of which resulted in complexes of the type [PhC≡W(NHMe2)(NMe2)(OR)2]. Full displacement of the amido ligands was also achieved in [PhC≡W(NHMe2){OC(CF3)2Me}{OSi(O-tBu)3}2] and [PhC≡W(NHMe2)(OSiPh3)3]. In addition, reaction of the three fluorinated alcohols with hexakis(dimethylamido)ditungsten yielded isomeric mixtures of bimetallic complexes [W2(NMe2)4(OR)2], which bear two electron-donating ligands and one electron-withdrawing ligand per tungsten atom. All amido-substituted compounds are active in the self-metathesis of 5-benzyloxy-2-pentyne, although [W2(OR)2(NMe2)4] complexes require longer initiation times depending on the degree of fluorination of the tert-butoxide ligand.

Synthesis and characterization of carbon- and nitrogen-centered (Z) trigonal prismatic tungsten clusters of the formula type A[W6ZCl 18]

Solid state reactions of tungsten(IV) chloride and carbodiimides (cyanamides) of lithium, sodium, calcium and silver yielded black crystalline powders of centered (Z) trigonal-prismatic tungsten cluster compounds having the general formula A[W6ZCl18] with A = Li, Na, Ca, Ag and Z = C, N. Crystal structures of the corresponding compounds were investigated by powder and single-crystal X-ray diffraction. The nature of the central atom was studied by mass spectrometry and nuclear magnetic resonance spectrometry. It turned out that the central atom can be C (in the case of the lithium and sodium compound) or N (in the case of the sodium and calcium compound).

Facile Reduction of Tungsten Halides with Nonconventional, Mild Reductants. I. Tungsten Tetrachloride: Several Convenient Solid-State Syntheses, a Solution Synthesis of Highly Reactive (WCI4)x, and the Molecular Structure of Polymeric Tungsten Tetrachloride

Polymeric (WCl4)X has been prepared in crystalline form from WCl6 by three new, safer solid-state approaches via mercury (in 83% yield), bismuth (82% yield), or antimony (97% yield) reduction. A modification of a published procedure for reduction of WCl6 with red phosphorus, which improves (WCl4)x purity, is also described. Highly reactive (WCl4)xpowder can be prepared in 99% yield via tin reduction of WCl6 in 1,2-dichloroethane. (WCl4)x powder was readily converted in high yields to the known WCl4(MeCN)2 and W2Cl4(OMe)4(HOMe)2. The molecular structure of (WCl4)x, as determined by single-crystal X-ray diffractometry, consists of a polymer of opposite-edge-sharing bioctahedra with alternating short (W(1)-W(1A), 2.688(2) ?) and long (W(1)?W(1B), 3.787(3) ?) tungsten - tungsten distances. The acute W(1)-Cl(2)-W(1A) angle (69.4(2)°), obtuse C1(1)-W(1)W(1A) angle (94.99(12)°), short axial Cl(1)?Cl(1A) nonbonded distance (3.085(10) ?, substantially less than twice the Cl van der Waals radius), and short W(1)-W(1A) distance are consistent with a strong W(1)-W(1A) interaction best described as a W=W bond for this d2-d2 compound. Crystal data: Cl4W, a = 11.782(3) ?, b = 6.475(1) ?, c = 8.062(2) ?, β= 131.14(1)°, V = 463.2(2) ?3, monoclinic, C2/m, Z = 4.

Two tungsten nitride chlorides: W2NCl8 and W 2NCl9

A solid state reaction of tungsten(VI)chloride and cyanamide yielded black crystals of W2NCl8 and red plate-like crystals of W 2NCl9. The structures of these compounds were determined by single crystal X-ray diffraction. The crystal structure of W 2NCl8 contains [Cl2/2Cl3WNWCl 3Cl2/2]-units forming chains along the c-axis. The tungsten atoms are linked by a symmetric nitrido bridge (d(W-N) = 1.8203(4) A). The crystal structure of W2NCl9 contains a dichloro-bridged dimer of a nitride-bridged ditungsten unit [Cl 5WNWCl3Cl2/2]2 with two different W-N distances of 1.726(9) A and 2.012(9) A.

Compounds with the electron-rich [W6Cl18] 2- cluster anion

Cluster compounds of the general formula A2[W6Cl 18] containing singly charged A cations (A = K, Rb, Ag, Tl, NH 4, N(C2H5)4, N(n-C3N 7)4, N(n-Cs

Unprecedented W2(0) quadruply bonded complex supported by π-donor ligands

A quadruply bonded complex W2(DippF)2K2 with a W2(0) core was synthesized and structurally characterized. The observed W-W distance of 2.407(1) ? and DFT calculations are consistent to the unprecedented electronic structure in D2h symmetry of σ2π2π2δ2 δ2δ?2 where the HOMO is the δ? orbital.

Salt-free reducing reagent of bis(trimethylsilyl)cyclohexadiene mediates multielectron reduction of chloride complexes of W(VI) and W(IV)

We developed a salt-free reduction of WCl6 using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) in toluene to give a low-valent trinulcear tungsten complex involving W(II) and W(III) centers, while in the presence of redox active ligands such as α-diketone and α-diimine the same reduction produced W(IV) complexes with the corresponding redox-active ligands, (α-diketone)WCl4 and (α-diimine)WCl4. A W(VI) complex with two α-diketone ligands, (α-diketone)2WCl2, was found to be synthetically equivalent to low-valent W(IV) species that trapped azopyridine to give (α-diketone)WCl2(azopyridine).