14040-11-0

Basic information

• Product Name: Tungsten hexacarbonyl
• Synonyms: TUNGSTEN CARBONYL;(OC-6-11)-Tungstencarbonyl;(oc-6-11)-tungstencarbonyl(w(co)6;Hexacarbonylwolfram;Tungsten carbonyl (W(CO)6);Tungsten carbonyl (W(CO)6), (OC-6-11)-;Tungstencarbonyl(W(CO)6);Tungstencarbonyl(W(CO)6),(OC-6-11)-
• CAS NO: 14040-11-0
• Molecular Formula: C₆O₆W
• Molecular Weight: 351.9
• EINECS: 237-880-2
• Product Categories: Catalysis and Inorganic Chemistry;Chemical Synthesis;Precursors by Metal;Tungsten;TungstenVapor Deposition Precursors;metal carbonyl complex;metal carbonyl complexes;ALD Precursors
• Mol File: 14040-11-0.mol
• Article Data: 116

Chemical Properties

• Melting Point: 150 °C(lit.)
• Boiling Point: 175 °C
• Flash Point: 200°C
• Appearance: Light yellow to beige/Fine Crystalline Powder
• Density: 2.65 g/mL at 25 °C(lit.)
• Vapor Density: 12.1 (vs air)
• Vapor Pressure: 1.2 mm Hg ( 67 °C)
• Storage Temp.: Store below +30°C.
• Water Solubility: insoluble
• Stability: Stable. Incompatible with oxidizing agents.
• CAS DataBase Reference: Tungsten hexacarbonyl(CAS DataBase Reference)
• NIST Chemistry Reference: Tungsten hexacarbonyl(14040-11-0)
• EPA Substance Registry System: Tungsten hexacarbonyl(14040-11-0)

Safety Data

• Hazard Codes: T
• Statements: 23/24/25
• Safety Statements: 22-24/25-45-38-36/37/39-28A-36/37
• RIDADR: UN 3466 6.1/PG 3
• WGK Germany: 3
• RTECS: YO7705000
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 14040-11-0(Hazardous Substances Data)

Usage

Description

Tungsten hexacarbonyl, with the chemical formula W(CO)6, is a white, volatile, and highly refractive crystalline solid. It has an atomic number of 74 and is easily vaporized and decomposed by electron beams, making it a convenient source of tungsten atoms. Tungsten hexacarbonyl is relatively air-stable and sparingly soluble in non-polar organic solvents. Its reactions typically begin with the displacement of some of its CO ligands, and it is similar to Mo(CO)6 in behavior, forming compounds that are kinetically more robust.

Uses

1. Used in Carbonylation Amines:
Tungsten hexacarbonyl is used as a catalyst in carbonylation amines for facilitating chemical reactions and improving the efficiency of the process.
2. Used in Tungsten Coatings on Base Metals:
Tungsten hexacarbonyl is used as a stable source of tungsten atoms through electron beam-induced deposition and decomposition of the carbonyl, allowing for the formation of tungsten coatings on base metals.
3. Used in Gas Sensor Applications:
Tungsten hexacarbonyl may be used as a precursor for the deposition of WO3-x films, which can be utilized as gas sensors for the detection of NO2.
4. Used in Fischer Carbene Complex:
Tungsten hexacarbonyl serves as a precursor to a Fischer carbene complex, which reduces Pd(II) to nanoparticulate Pd(0) that is catalytically active in Hiyama cross-coupling.
5. Used in Electron Beam-Induced Deposition Processes:
Due to its easy vaporization and decomposition by electron beams, tungsten hexacarbonyl is widely used in electron beam-induced deposition processes.
Physical Properties:
Tungsten hexacarbonyl is a white crystalline solid with a density of 2.65 g/cm3. It decomposes at 170°C without melting and sublimes. The vapor pressure is 0.1 torr at 20°C. It is insoluble in water but soluble in most organic solvents.
Chemical Properties:
Tungsten hexacarbonyl is a white, volatile, highly refractive crystalline solid that decomposes without melting at 150°C. It is one of the more stable carbonyls, insoluble in water, and soluble in organic solvents.

Reaction

Volatile starting material used for the atomic layer deposition of tungsten oxide, tungsten nitride. Tungsten hexacarbonyl is used to produce tungsten coatings on base metals. This is done by deposition of the carbonyl on the metal surface, which decomposes to leave a tungsten coating.

Preparation

Tungsten hexacarbonyl is produced by heating tungsten metal with carbon monoxide at high pressure. Also, carbonyl can be prepared by reducing the tungsten hexachloride by heating with iron powder under carbon monoxide pressure.

Health Hazard

Toxicity of this compound is not reported.Although air stable at ambient temperature,upon heating it emits toxic carbonmonoxide. Chronic exposure to its vaporsor dusts can cause bronchitis. Ingestion islikely to produce the toxic effect of tungstenoxides.

Fire Hazard

It explodes when heated to high temperature. Solution in ether can explode if stored for a long time.

Purification Methods

Sublime it in vacuo before use [Connoe et al. J Chem Soc, Dalton Trans 511 1986]. TOXIC.

InChI:InChI=1/6CH2O.W/c6*1-2;/h6*1H2;

Synthetic route

tetrakis(acetonitrile)copper(I)tetrafluoroborate + pentacarbonyl(1,3-diethylimidazolin-2-ylidene)tungsten(0) + carbon monoxide (201230-82-2) + 1,2-bis-(diphenylphosphino)ethane (1663-45-2) → tungsten hexacarbonyl (14040-11-0) + [ Cu(1,2-bis(diphenylphosphino)ethane)2]BF4 (147892-57-7)

Conditions	Yield
N2-atmosphere; 3 equiv. of phosphine;	A 60% B 99%

(CO)5WC(OEt)SiPh3 → tungsten hexacarbonyl (14040-11-0) + triphenylhydroxysilane (791-31-1)

Conditions	Yield
With carbon monoxide In diethyl ether High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 96%
With carbon monoxide In pentane High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 96%

pentacarbonyl(N-ethyl-N'-pentacarbonyltungsten-3-hydropyrimidine-1,2-propadienylidene)tungsten → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl(N-ethyl-3-hydropyrimidine-1,2-propadienylidene)tungsten

Conditions	Yield
With air In dichloromethane (N2); a soln. of W complex exposed to air for 120 min; evapd. (vac.), chromd. (silica, CH2Cl2);	A n/a B 96%

(CO)5WC(OEt)SiPh3 → tungsten hexacarbonyl (14040-11-0) + Ph3Si(EtO)CHCOOH

Conditions	Yield
With carbon monoxide; water In acetone High Pressure; under nitrogen; autoclave: 50 atm CO-pressure, 70 h, room temperature;; evaporation, chromatography (silicagel, petroleum ether/ether), recrystd.;	A n/a B 95%

tetrabutylammonium {1-η-trans-6-hydroxy-6,7,7-trimethyl-1-oxo-3-octen-1-yl}pentacarbonyltungstate(0) (126823-74-3) + triethyloxonium fluoroborate (368-39-8) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl{ethoxy(trans-5-hydroxy-5,6,6-trimethyl-2-hepten-1-yl)carbene}tungsten (126823-75-4)

Conditions	Yield
In dichloromethane Ar atmosphere; stirring (0°C, 1 h); removal of solvent (vac.), addn. of n-hexane, stirring (1 h), filtration, pptn. of W(CO)6 on concn. and cooling (-30°C), decantation, evapn. of soln. to dryness;	A n/a B 91%

(tungstenpentacarbonyl)2(μ-CH3OCCH(C3H7)CH2C(CH3)(CH2CHCH2)COCH3) (115677-62-8) → tungsten hexacarbonyl (14040-11-0) + (η(6)-benzene)tungsten(0) tricarbonyl (12128-53-9) + C(CH3)(CH2CHCH2)C(OCH3)C(OCH3)CH(C2H4CH3)CH2

Conditions	Yield
In benzene-d6 heating 3 h in benzene at 75°C; identification of organometallic products by (13)C NMR;	A n/a B n/a C 90%
In benzene heating 3 h in benzene at 75°C; identification of organometallic products by (13)C NMR;	A n/a B n/a C 90%

(CO)5WC(OEt)SiPh3 + benzylidene phenylamine (538-51-2) → tungsten hexacarbonyl (14040-11-0) + CH(C6H5)CSi(C6H5)3(C2H5O)CON(C6H5) + CH(C6H5)CSi(C6H5)3(C2H5O)CON(C6H5) + triphenylhydroxysilane (791-31-1)

Conditions	Yield
With carbon monoxide In diethyl ether High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B n/a C n/a D 90%

dicobalt octacarbonyl (15226-74-1, 61091-28-9, 61117-58-6) + {MoW(C8H7)(CO)7(C5H5)} → tungsten hexacarbonyl (14040-11-0) + {MoCo2(μ3-CC6H4Me-4)(CO)8(η-C5H5)}

Conditions	Yield
In petroleum ether MoW(CC6H4Me-4)(CO)7(C5H5) in light petroleum treated with Co2(CO)8, refluxed for 1 h; evapd. in vac., chromd. (Al2O3, CH2Cl2-light petroleum (1:4)), evapd. in vac.; elem. anal.;	A n/a B 90%

pentacarbonyl{4-cycloheptatrienyl-1-(diethylamino)-3-ethoxy-2-methyl-2E-butenylidene}tungsten (140834-40-8) → tungsten hexacarbonyl (14040-11-0) + (pentacarbonyl)(diethylamino)tungsten (33846-96-7)

Conditions	Yield
In toluene byproducts: 3-ethoxy-2-methyl-5H-benzocycloheptatriene, 2-ethoxy-3-methyl-5H-benzocycloheptatriene, 2-ethoxy-3-methyl-7H-benzocycloheptatriene; inert atmosphere; heating (5 h, 100°C); chromy. (silica gel, petroleum ether/CH2Cl2 4:1); elem. anal.;	A n/a B 88%

pentacarbonyl{2-(cyclohepta-2,4,6-trien-1-yl)-1-ethoxyethylidene}tungsten (137125-09-8) + (E)-N,N-dimethylcinnamamide (17431-39-9) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl((3-(2,4,6-cycloheptatrienyl)-2-ethoxy-4-phenyl-1-cyclobutenyl)(dimethylamino)methylene)tungsten

Conditions	Yield
With phosphorus oxychloride; triethylamine In dichloromethane under Ar atm. to N,N-dimethyl-3-phenylacrylamide in CH2Cl2 was added POCl3 and stirred at 0°C for 30 min, W complex and NEt3 in CH2Cl2 were added, 20°C, 16 h; react. mixt. was evapd. at 20°C, residue was dissolved in CH2Cl2 and chromed. on silica; diastereomers were not isolated;	A n/a B 86%

2Na(1+)*W(CO)5(2-) = Na2[W(CO)5] (54099-82-0) + carbon dioxide (124-38-9) → tungsten hexacarbonyl (14040-11-0) + sodium carbonate (497-19-8)

Conditions	Yield
In tetrahydrofuran reductive disproportionation; mechanism discussed;; IR;;	A 83% B n/a
In tetrahydrofuran soln. of the W-compound was treated with gasous CO2 at -78°C, warmed to 25°C; solvent removed (vac.), extd. (diethyl ether), ether removed (vac.); IR, MAS;	A 83% B n/a

2Li(1+)*W(CO)5(2-)=Li2{W(CO)5} + carbon dioxide (124-38-9) → tungsten hexacarbonyl (14040-11-0) + lithium carbonate (554-13-2)

Conditions	Yield
In tetrahydrofuran reductive disproportionation; mechanism discussed;; IR;;	A 82% B 74%
In tetrahydrofuran soln. of the W-compound was treated with gasous CO2 at -78°C, warmed to 25°C; solvent removed (vac.), extd. (diethyl ether), ether removed (vac.); IR, MAS;	A 82% B 74%

(CO)5WOs(CO)4(P(CH3)3) (89579-58-8, 144299-40-1, 89617-67-4) → tungsten hexacarbonyl (14040-11-0) + osmium(carbonyl)4(P(methyl)3) (89579-59-9)

Conditions	Yield
In benzene Irradiation (UV/VIS); irradn. (λ > 400 nm); detd. by IR spectroscopy;	A 66% B 82%

(CO)5WOs(CO)4(P(CH3)3) (89579-58-8, 144299-40-1, 89617-67-4) + triphenylphosphine (603-35-0) → tungsten hexacarbonyl (14040-11-0) + triphenylphosphine tungsten pentacarbonyl (15444-65-2) + Os(CO)3(P(CH3)3)(P(C6H5)3) (158274-60-3) + osmium(carbonyl)4(P(methyl)3) (89579-59-9)

Conditions	Yield
In benzene Irradiation (UV/VIS); irradn. (λ > 400 nm); detd. by IR spectroscopy;	A 8% B 81% C 49% D 46%

dimethyl amine (124-40-3) + (SR)-pentacarbonyl-(5-methoxy-5-phenyl-2(5H)-furanylidene)tungsten(0) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl-dimethylamine-tungsten (15228-31-6)

Conditions	Yield
In dichloromethane byproducts: 5,5'-diphenyl-2,2'-bifuran; Ar atmosphere, addn. of Me2NH to soln. of W complex at -78°C, warming to room temp., stirring (1 d); removement of solvent, column chromy. (silica gel, elution of W(CO)6 andorganic byproduct with petroleum ether (fraction 40.60°C)/CH2Cl2 (3:1), elution of (Me2NH)W(CO)5 with petroleum ether (fraction 40-60.de gree.C)/CH2Cl2 (1:1));	A 8% B 80%

η5-indenylbis(ethylene)rhodium(I) + {CoW(CC6H4CH3)(CO)8} → tungsten hexacarbonyl (14040-11-0) + {CoRh2(CC6H4CH3)(CO)4(C9H7)2} + {tricobalt(μ3-p-tolylmethylidyne)nonacarbonyl}

Conditions	Yield
With CO In petroleum ether light petroleum soln. of Rh(C2H4)2(C9H7) treated with CO gas (15 min), solid CoW(CC6H4Me-4)(CO)8 added, stirred for 12 h; evapd. in vac., chromd. (Al2O3, CH2Cl2-light petroleum (1:2)), evapd. in vac., crystd. from CH2Cl2-light petroleum (1:10); elem. anal.;	A n/a B 80% C <1

2-ethynyl-quinoline (40176-78-1) + tungsten pentacarbonyl tetrahydrofuran (36477-75-5) + triethyloxonium fluoroborate (368-39-8) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl(N-ethyl-3-hydroquinoline-1,2-propadienylidene)tungsten

Conditions

Yield

With n-BuLi In dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-80°C, 20 min); W complex in THF added; stirred (ambienttemp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Et3O BF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3); elem. anal.;

A n/a B 80%

(CO)5WC(OCH2CH2CHCHOCH3)C6H4CH3 + triphenylphosphine (603-35-0) → tungsten hexacarbonyl (14040-11-0) + W(CO)4((C6H5)3P)2 (16743-03-6, 38800-77-0, 68738-00-1) + triphenylphosphine tungsten pentacarbonyl (15444-65-2) + 1-(4-methylphenyl)-2-oxa-6-exo-methoxybicyclo<3.1.0>hexane + 1-(4-methylphenyl)-2-oxa-6-endo-methoxybicyclo<3.1.0>hexane

Conditions	Yield
In benzene-d6 thermal decompn. (45°C/6 h/sealed tube);; (CO)5WPPh3 isolated by thin layer chromy. (SiO2/hexane);;	A n/a B n/a C 79% D n/a E n/a

dipotassium pentacarbonyltungstate(-II) + carbon dioxide (124-38-9) → tungsten hexacarbonyl (14040-11-0) + potassium carbonate (584-08-7)

Conditions	Yield
In tetrahydrofuran reductive disproportionation;; IR;;	A 48% B 78%

pentacarbonyl(2-N,N-diethylamino-3,3-diphenyl-telluro-2-propenic acid-N,N-diethylamide)tungsten → tellurium + tungsten hexacarbonyl (14040-11-0) + (C2H5)2NCHC(N(C2H5)2)CH(C6H5)2 (122420-18-2)

Conditions	Yield
With carbon monoxide In diethyl ether (CO)5WTeC(Ph)C(NEt2)CPh2 in ether with CO pressure of 100 bar, 18 h at 60°C; chromy. (silicagel, pentane/CH2Cl2) at -20°C;	A n/a B n/a C 77%

trans-(NO)(CO)4WBr + (cyclohexyl)2PCH2CH2PPh2 (122425-32-5) → tungsten hexacarbonyl (14040-11-0) + (Cy2PCH2CH2PPh2)(CO)2(NO)WBr

Conditions	Yield
In tetrahydrofuran heating at reflux, 40 min; warming under vac. (removal of solvent and W(CO)6), chromy. over a silica column with 3:1 benzene-hexane, elem. anal.;	A n/a B 75%

pentacarbonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten + methyl(diethylamino)acetylene (4231-35-0) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl{diethylamino(E-β-ethoxy-α-methyl-β-phenylethinylvinyl)carbene}tungsten + pentacarbonyl{diethylamino(Z-β-ethoxy-α-methyl-β-phenylethinylvinyl)carbene}tungsten

Conditions	Yield
In dichloromethane under N2, 40 min at 0°C; removal of solvent in vac., chromy. on silica gel (petroleum ether/CH2Cl2 (2:1), 0°C), removal of solvent in vac., recrystn. (petroleum ether/toluene 5:1); elem. anal.;	A n/a B 75% C 10%

(CO)5WC(OEt)SiPh3 + N-Benzylidenemethylamine (622-29-7) → tungsten hexacarbonyl (14040-11-0) + CH(C6H5)CSi(C6H5)3(C2H5O)CON(CH3) + CH(C6H5)CSi(C6H5)3(C2H5O)CON(CH3) + triphenylhydroxysilane (791-31-1)

Conditions	Yield
With carbon monoxide In diethyl ether High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 74% C 16% D 5%

tungsten(pentacarbonyl)(diethylaminocarbene-SiPh2Me) → tungsten hexacarbonyl (14040-11-0) + tungsten(tetracarbonyl)(diethylaminocarbene)SiPh2Me

Conditions	Yield
In neat (no solvent, solid phase) slow heating of carbene complex in a Schlenk tube at 2.00 Torr and 110°C, melting with formation of bubbles; pptn. of W(CO)6 on cool parts of tube, dissolution of melt in ether/petroleum ether, chromy. on silica at -20°C with ether/petroleum ether, elution of orange part with ether, spect. detected;	A n/a B 74%

1,10-Phenanthroline (66-71-7) + disodium dichlorobis(pentacarbonyltungsten)stannate(II) → tungsten hexacarbonyl (14040-11-0) + bis(pentacarbonyltungsten)(1,10-phenanthroline)tin (209454-47-7) + tetracarbonyl(1,10-phenanthroline)tungsten(0) (14729-20-5)

Conditions	Yield
In tetrahydrofuran byproducts: NaCl; Ar atmosphere, addn. of solid ligand to THF soln. of metal complex at 20°C, stirring (20°C, 30 min); removement of solvent (vacuum), dissolution (THF), chromy. (silica gel, elution of byproducts with Et2O, elution of main product with THF), evapn. to dryness; elem. anal.;	A n/a B 71% C n/a

2-ethynyl-quinoline (40176-78-1) + tungsten pentacarbonyl tetrahydrofuran (36477-75-5) + trimethoxonium tetrafluoroborate (420-37-1) → tungsten hexacarbonyl (14040-11-0) + pentacarbonyl(N-methyl-3-hydroquinoline-1,2-propadienylidene)tungsten

Conditions

Yield

With n-BuLi In dichloromethane under N2 or Ar; n-BuLi in hexane added (-80°C) to alkyne in THF; stirred (-80°C, 20 min); W complex in THF added; stirred (ambienttemp., 30 min); solvent removed; dissolved in CH2Cl2; treated with Me3O BF4 (0°C); stirred (60 min); filtered at -20°C through silica layer using CH2Cl2 as eluent; solvent evapd.; sepd. by chromy. (silica, -20°C, pentane-CH2Cl2 2:1, 1:1 to 1:3); elem. anal.;

A n/a B 71%

1,1,2,2,3,3,3,3,3-nonacarbonyl-1,2-bis(η5-cyclopentadienyl)-μ3-[sulphido(thiocarbonyl)-C-(Fe1)S(Fe2)S(W3)]-di-irontungsten → di(cyclopentadienideiron dicarbonyl) (38117-54-3) + tungsten hexacarbonyl (14040-11-0) + ((OC)(η-C5H5)-FeSC(Fe(η-C5H5)(CO)2)S-) (cyclic)

Conditions	Yield
In dichloromethane under N2, complex in CH2Cl2 was refluxed for 4 h; soln. was evapd., residue was chromd.; products were analized by NMR, IR;	A n/a B n/a C 70%

tungsten(pentacarbonyl)(diethylaminocarbene-SiPh3) → tungsten hexacarbonyl (14040-11-0) + tungsten(tetracarbonyl)(diethylaminocarbene)SiPh3

Conditions	Yield
In neat (no solvent, solid phase) slow heating of carbene complex in a Schlenk tube at 0.50 Torr and 125°C, melting with formation of bubbles; pptn. of W(CO)6 on cool parts of tube, dissolution of melt in ether/petroleum ether, chromy. on silica at -20°C with ether/petroleum ether, elution of orange part with ether, recrystn. from ether/pentane, elem. anal.;	A n/a B 70%

tungsten pentacarbonyl tetrahydrofuran (36477-75-5) + [Fe2(CO)2(Cp)2(μ-CO)(μ-C(CN)2)] → tungsten hexacarbonyl (14040-11-0) + {(FeCp(CO))2(μ-CO)(μ-C(CN)(CNW(CO)5))} + {(FeCp(CO))2(μ-CO)(μ-C(CNW(CO)5)2)}

Conditions	Yield
In tetrahydrofuran byproducts: Me2S; under N2; W-complex in THF added to Fe-complex in THF, stirred overnight at room temp.; dried (vac.), dissolved in CH2Cl2, chromy. (alumina; eluent: CH2Cl2:petrolether = 1:1 (v/v)), crystn.;	A n/a B 70% C n/a

chloro(1,5-cyclooctadiene)rhodium(I) dimer + pentacarbonyl[1-ethoxy-2-(1,2-diphenylethenyl)-4-(1,3,3-trimethylindolin-2-ylidene)but-2-en-1-ylidene]tungsten → tungsten hexacarbonyl (14040-11-0) + η4-cyclooctadiene[1-ethoxy-2-(1,2-diphenylethenyl)-4-(1,3,3-trimethylindolin-2-ylidene)but-2-en-1-ylidene]rhodium chloride

Conditions	Yield
In dichloromethane CH2Cl2, 20°C, 1.5 h; flash chromy. (silica gel, pentane/diethylether (1/1)); elem. anal.;	A n/a B 69%
In (2)H8-toluene toluene-d8, 30°C, 1 h; not sepd., detected by NMR spectroscopy;

tungsten hexacarbonyl (14040-11-0) + 1,1',3,3'-tetramethyl-2,2'-biimidazolidinylidene (1911-01-9) → cis-tetracarbonylbis(1,3-dimethyl-4-imidazolidin-2-ylidene)tungsten(0) (64514-96-1)

Conditions	Yield
In decalin byproducts: CO; inert atmosphere; excess olefin, > 180°C; elem. anal.;	100%

tungsten hexacarbonyl (14040-11-0) + acetonitrile (75-05-8) → bis(acetonitrile)diiodotricarbonyltungsten(II) (113350-36-0, 102382-37-6)

Conditions	Yield
With iodine In acetonitrile under Ar, a suspension of W(CO)6 in NCCH3 refluxed (72 h), cooled (0°C), I2 added; solvent removed (vac.), crystn.; elem. anal.;	100%

tungsten hexacarbonyl (14040-11-0) + benzyl azide (622-79-7) → (bezylisocyanide)pentacarbonyltungsten (77826-99-4)

Conditions	Yield
With triphenylphosphine In tetrahydrofuran stirring, 25°C, 10 h;	100%

tungsten hexacarbonyl (14040-11-0) + 1,2-bis-(diphenylphosphino)ethane (1663-45-2) → tetracarbonyl-1,2-bis(diphenylphosphino)ethane-tungsten(0) (29890-05-9) + {μ-bis(diphenylphosphino)ethane}-bis{pentacarbonyltungsten(0)} (15413-06-6)

Conditions	Yield
With trimethylamine-N-oxide In acetonitrile W(CO)6 and Me3NO stirred in MeCN (20°C, 30 min, under nitrogen), addn. of diphosphine (molar ratio W(CO)6 : phosphine = 2:1), heated (75°C, 16 h), soln. pumped to dryness; washed with hexane; 31P-NMR;	A 0% B 100%

tungsten hexacarbonyl (14040-11-0) + 2,2'-Bipyrimidine (34671-83-5) → (μ-2,2'-bipyrimidine){W(CO)4}2 (85853-75-4)

Conditions	Yield
In xylene mixt. W(CO)6 and bpym in xylene heated at reflux for 4 h under N2; soln. cooled to room temp., crystals filtered, washed with acetonitrileand petroleum ether and dried under vac.; elem. anal.;	100%

tungsten hexacarbonyl (14040-11-0) + 2-(2-pyridyl)-4-(4-fluorophenyl)-6-phenylphosphinine (1616764-99-8) → 2-(2-pyridyl)-4-phenyl-6-(4-fluorophenyl)phosphinine-P,N-tungsten tetracarbonyl (1616765-11-7)

Conditions	Yield
In tetrahydrofuran-d8 UV-irradiation; Inert atmosphere; Sealed tube;	100%
In tetrahydrofuran-d8 UV-irradiation;

tungsten hexacarbonyl (14040-11-0) + 2-(2-pyridyl)-4-(4-trifluoromethylphenyl)-6-phenylphosphinine (1616765-00-4) → 2-(2-pyridyl)-4-phenyl-6-(4-trifluoromethylphenyl)phosphinine-P,N-tungsten tetracarbonyl (1616765-12-8)

Conditions	Yield
In tetrahydrofuran-d8 UV-irradiation; Inert atmosphere; Sealed tube;	100%
In tetrahydrofuran-d8 UV-irradiation;

tungsten hexacarbonyl (14040-11-0) + 2-(2-pyridyl)-4-(4-methylthiophenyl)-6-phenylphosphinine (1616765-01-5) → 2-(2-pyridyl)-4-phenyl-6-(4-methylthiophenyl)phosphinine-P,N-tungsten tetracarbonyl (1616765-13-9)

Conditions	Yield
In tetrahydrofuran-d8 UV-irradiation; Inert atmosphere; Sealed tube;	100%
In tetrahydrofuran-d8 UV-irradiation;

2-(2-pyridyl)-4,6-diphenyl-λ3-phosphinine + tungsten hexacarbonyl (14040-11-0) → 2-(2-pyridyl)-4,6-diphenylphosphinine-P,N-tungsten tetracarbonyl (1616765-10-6)

Conditions	Yield
In tetrahydrofuran-d8 UV-irradiation; Inert atmosphere; Sealed tube;	100%
In tetrahydrofuran-d8 at 20℃; for 12h; Inert atmosphere; Schlenk technique; Glovebox; UV-irradiation;	58%
In tetrahydrofuran-d8 UV-irradiation;
In toluene at 120℃; Inert atmosphere; Schlenk technique; Glovebox;

tungsten hexacarbonyl (14040-11-0) + 4,6-diphenyl-[2,2']bipyridinyl (57476-59-2) → [W(CO)4(2-(2’-pyridyl)-4,6-diphenylpyridine)]

Conditions	Yield
In tetrahydrofuran-d8 for 24h; UV-irradiation; Inert atmosphere; Sealed tube;	100%
In tetrahydrofuran-d8 at 20℃; for 48h; Inert atmosphere; Schlenk technique; Glovebox; UV-irradiation;	70%
In toluene at 120℃; Inert atmosphere; Schlenk technique; Glovebox;

tungsten hexacarbonyl (14040-11-0) + 3-diphenylphosphino-2-methylpropionitrile → [(CO)4W(C6H5)2PCH2CH(CH3)CH2NH2]*0.25CH2Cl2

Conditions	Yield
With sodium tetrahydroborate; dichloromethane In ethanol N2; addn. of 10.0 mmol W(CO)6, 10.0 mmol ligand and 60.3 mmol NaBH4 to hot ethanol; refluxing for 14 h; removal of C2H5OH; shaking with H2O/CH2Cl2; separation of CH2Cl2 layer;drying over MgSO4; filtration; evapn. to dryness; elem. anal.;	99.2%
With sodium tetrahydroborate; dichloromethane In ethanol N2; addn. of 10.0 mmol W(CO)6, 10.0 mmol ligand and 60.3 mmol NaBH4 to hot ethanol; refluxing for 14 h; removal of C2H5OH; shaking with H2O/CH2Cl2; separation of CH2Cl2 layer;drying over anhydrous MgSO4; filtration; evapn. to dryness; refluxing in CH2Cl2 under N2; addn. of hexane; evapn. till slight cloudiness; cooling to -10°C; elem. anal.;	78%

tungsten hexacarbonyl (14040-11-0) + phenol (108-95-2) → tungsten hexaphenoxide (799823-45-3)

Conditions	Yield
In further solvent(s) air-free techniques; refluxed;	99%

tungsten hexacarbonyl (14040-11-0) + tris(2-pyridyl)methane (77429-58-4) → (tri-2-pyridylmethane)tricarbonyltungsten (132079-48-2)

Conditions	Yield
In acetonitrile N2 atmosphere; refluxing of W(CO)6 in MeCN (48 h), addn. of ligand, refluxing (12 h); sepn. (decantation), washing (CH2Cl2), drying (vac., overnight); elem. anal.;	99%

tungsten hexacarbonyl (14040-11-0) + acetone (67-64-1) + 1,2-bis-(diphenylphosphino)ethane (1663-45-2) → fac-[W(CO)3(1,2-bis(diphenylphosphino)ethane)(Me2CO)] (87900-84-3, 84411-66-5)

Conditions	Yield
In acetone Irradiation (UV/VIS); N2-atmosphere; irradn. (450 W Hg lamp, 10 h); evapn. (vac.), washing (hexane / Et2O = 3 : 1), drying (vac.);	99%

tungsten hexacarbonyl (14040-11-0) + Ti(Si(CH3)2C6H5N)3N3C6H12(1+)*I(1-)*C6H5Br=Ti(Si(CH3)2C6H5N)3N3C6H12I*C6H5Br → Ti(Si(CH3)2C6H5N)3N3C6H12(1+)*W(CO)5I(1-)=Ti(Si(CH3)2C6H5N)3N3C6H12W(CO)5I

Conditions	Yield
In tetrahydrofuran a THF-soln. of W(CO)6 was added at room temp. to a dispersion of Ti-complex in THF, the mixt. was warmed at 70°C for 4 days, cooled (N2); filtered, the solvent and an excess of W(CO)6 were removed in vac., extd. with CH3CN, cooled to -20°C; elem. anal.;	99%

tetrahydrofuran (109-99-9) + tungsten hexacarbonyl (14040-11-0) + trans-1,2-dihydro-1,2-diphenyl-naphtho[1,8-c,d]-1,2-diphosphole → (OC)5W(μ-trans-1,2-dihydro-1,2-diphenyl-naphtho[1,8-c,d]-1,2-diphosphole)W(CO)5

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); (N2); a soln. of W complex irradiated with a Hg lamp for 2.5 h, a soln. of ligand added, stirred overnight; THF-removed (vac.), dissolved in CHCl3, passed through a silica gel column, chromd. (GPC); elem. anal.;	99%

((CH3)2NB)2(NC6H3(CH(CH3)2)2)2C (850816-24-9) + tungsten hexacarbonyl (14040-11-0) → ((CH3)2NB)2(NC6H3(CH(CH3)2)2)2CW(CO)5

Conditions	Yield
In benzene Irradiation (UV/VIS); C6H6, UV-promoted; crystd. from benzene;	99%

tetrahydrofuran (109-99-9) + tungsten hexacarbonyl (14040-11-0) + (CO)5W(P(CH2NMe)3P) (956736-32-6) → (CO)5W(P(CH2NMe)3P)W(CO)5 (956736-33-7)

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); irradiation of THF soln. of tungsten hexacarbonyl for 12 h with 450 W water cooled UV immersion lamp, addn. to stirred soln. of phosphorus compd. in THF, stirring for 24 h; evapn., heating at 70°C at 300 mTorr, dissolving in THF, addn. ofpentane, filtration, drying in vac., elem. anal.;	99%

tetrahydrofuran (109-99-9) + 2,6-diisocyano-1,3-diethoxycarbonylazulene (880260-90-2) + tungsten hexacarbonyl (14040-11-0) → [(OC)5W(2,6-diisocyano-1,3-diethoxycarbonylazulene)W(CO)5] (880260-97-9)

Conditions	Yield
In tetrahydrofuran Irradiation (UV/VIS); (Ar); a soln. of W complex photolyzed, added to a soln. of ligand dropwise at room temp., stirred; evapd. (vac.), sublimed at 1E-2 Torr at 40°C, chromd. (silica gel, CHCl3), solvent-removed, dried at 1E-2 Torr; elem. anal.;	99%

tungsten hexacarbonyl (14040-11-0) + 8,16,24,32-tetraisocyano[2.2.2.2]metacyclophane (105591-98-8) → [(CO)5W]4(μ4-η1:η1:η1:η1-8,16,24,32-tetraisocyano[2.2.2.2]metacyclophane) (1020194-73-3)

Conditions	Yield
With THF In tetrahydrofuran Irradiation (UV/VIS); (Ar); soln. of W complex in THF was photolyzed for 4 h; transferred dropwise to soln. of ligand at room temp.; stirred for 15 h; solvent removed (vac.); chromd. (silica gel, CH2Cl2); solvent removed; dried (vac.); elem. anal.;	99%

tungsten hexacarbonyl (14040-11-0) + 18-crown-6 ether (17455-13-9) + Si(SiMe2Pz(tBu))4 (1299293-95-0) → [W(CO)5(Si(Si(CH3)2C3H2N2C4H9)3K(CH2CH2O)6)]

Conditions	Yield
With tBuOK In tetrahydrofuran byproducts: CO; at room temp.; NMR, IR;	99%

tungsten hexacarbonyl (14040-11-0) + Si(Si(CH3)2C3H2N2C4H9)3K(CH2CH2O)6 → [W(CO)5(Si(Si(CH3)2C3H2N2C4H9)3K(CH2CH2O)6)]

Conditions	Yield
In tetrahydrofuran at room temp.; NMR, IR;	99%

tungsten hexacarbonyl (14040-11-0) + potassium cyclopentadiene → lithium tricarbonyl(η5-cyclopentadienyl)tungstate

Conditions	Yield
In 1,2-dimethoxyethane (Ar); refluxing 1:1 mixt. of potassium cyclopentadienide and tungsten compd. in DME for 40 h; filtration, evapn., addn. of hexane, sonication, evapn., drying at 50°C in vac. for 4 h, NMR and IR;	99%

tungsten hexacarbonyl (14040-11-0) + N-methyl-N-nitrosotoluene-p-sulfonamide (80-11-5) + C12H19Na → [(η5-C5Me4nPr)W(NO)(CO)2]

Conditions	Yield
Stage #1: tungsten hexacarbonyl; C12H19Na In tetrahydrofuran at 78℃; for 96h; Stage #2: N-methyl-N-nitrosotoluene-p-sulfonamide In tetrahydrofuran for 2h;	99%

tungsten hexacarbonyl (14040-11-0) + 4-chlorobenzonitrile (100-00-5) + carbonic acid dimethyl ester (616-38-6) → N-(4-chlorophenyl)acetamide (539-03-7)

Conditions	Yield
With di(rhodium)tetracarbonyl dichloride; 1,3-bis-(diphenylphosphino)propane; sodium phosphate; sodium iodide In water at 120℃; for 24h; Inert atmosphere; Sealed tube;	99%

tungsten hexacarbonyl (14040-11-0) + 1-methyl-3-nitrobenzene (99-08-1) + carbonic acid dimethyl ester (616-38-6) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With di(rhodium)tetracarbonyl dichloride; 1,3-bis-(diphenylphosphino)propane; sodium phosphate; sodium iodide In water at 120℃; for 24h; Inert atmosphere; Sealed tube;	99%

tungsten hexacarbonyl (14040-11-0) + carbonic acid dimethyl ester (616-38-6) + 1-ethoxy-4-nitrobenzene (100-29-8) → 4-ethoxyacetanilide (62-44-2)

Conditions	Yield
With di(rhodium)tetracarbonyl dichloride; 1,3-bis-(diphenylphosphino)propane; sodium phosphate; sodium iodide In water at 120℃; for 24h; Inert atmosphere; Sealed tube;	99%

tungsten hexacarbonyl (14040-11-0) → trans-triphenylphosphane tetracarbonyltungsten (16743-03-6, 38800-77-0, 68738-00-1)

Conditions	Yield
With triphenylphosphine In ethanol; water under N2, W(CO)6, NaBH4 and PPh3 suspended in 95%EtOH at room temp., mixt. refluxed and stirred vigorously for 12h; cooled, filtered, washed (water, hot EtOH, acetone, pentane);	98%

tungsten hexacarbonyl (14040-11-0) + iodine(I) bromide (7789-33-5) + acetonitrile (75-05-8) → WBrI(CO)3(NCCH3)2 (127340-84-5)

Conditions	Yield
In acetonitrile N2-atmosphere; refluxing of W(CO)6 (72 h), then BrI addn. at 0°C, stirring (30 min); solvent evapn. (vac.); elem. anal.;	98%

Upstream product

• 36477-75-5 tungsten pentacarbonyl tetrahydrofuran 
• 64-69-7 Iodoacetic acid 
• 99193-49-4 (W(CO)5((CH₃)3SiCH₂SCH₂Si(CH₃)3)) 
• 99193-48-3 (W(CO)5((CH₃)3SiCH₂SeCH₂Si(CH₃)3)) 
• 32610-90-5 [W(η(5)-C5H5)(CO)2(N:CBu(t)2)] 
• 36562-36-4 [W(η(5)-C5H5)(CO)2(N:C(p-MeC6H4)2)] 
• 30395-19-8 W(CO)5 
• 201230-82-2 carbon monoxide 
• 1641-69-6 [13C]Carbon monoxide 
• 60166-30-5 W(CO)5(4-acetyl-pyridine) 
• 115677-62-8 (tungstenpentacarbonyl)2(μ-CH3OCCH(C3H7)CH2C(CH3)(CH2CHCH2)COCH3) 
• 180991-46-2 (triphos)Rh(η(3)-(CO)5W(2-vinylthiophenolate)) 
• 1333-74-0 hydrogen 
• 15444-65-2 triphenylphosphine tungsten pentacarbonyl 

Downstream Products

• 7783-82-6 tungsten(VI) fluoride 
• 91482-94-9 (tetraphenylphosphonium)[CpW(CO)3] 
• 168642-60-2 (tetraphenylphosphonium)[Cp(*)W(CO)3] 
• 799823-45-3 tungsten hexaphenoxide 
• 201230-82-2 carbon monoxide 
• 1333-74-0 hydrogen 
• 83801-05-2 tungsten (2,6-dimethylphenyl isocyanide)6 
• 16743-03-6 W(CO)4((C₆H₅)3P)2 
• 10028-15-6 ozone 
• 17712-55-9 (PPh₃)3W(CO)3 
• 16743-03-6 cis-triphenylphosphane tetracarbonyltungsten 
• 7440-33-7 tungsten 

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