13007-92-6

Usage

Reaction

Reagent for the preparation of Fischer carbenes. Reagent for the preparation of arenechromium complexes.

Chemical Properties

Different sources of media describe the Chemical Properties of 13007-92-6 differently. You can refer to the following data:
1. white crystals or powder
2. Chromium carbonyl is a colorless crystalline substance which sinters (forms a coherent mass without melting) @ 90°C.

Physical properties

White orthogonal crystal; density 1.77 g/cm3; sublimes at ordinary temperatures; vapor pressure 1 torr at 48°C; decomposes at 130°C; insoluble in water and alcohols; soluble in ether, chloroform and methylene chloride.

Uses

Different sources of media describe the Uses of 13007-92-6 differently. You can refer to the following data:
1. It is used as a catalyst for polymerization andisomerization of olefins. It is also used as anadditive to gasoline, to increase the octanenumber.
2. Chromiumhexacarbonyl is a volatile; air stable precursor of Chromium(0); widely used for thin film deposition - ALD and CVD. The thin films can be grown at room temperature and low pressure by laser CVD .
3. In catalysts for olefin polymerization and isomerization; gasoline additive to increase octane number; preparation of chromous oxide, CrO.

Preparation

Chromium hexacarbonyl is prepared by the reaction of anhydrous chromium(III) chloride with carbon monoxide in the presence of a Grignard reagent. A 60% product yield may be obtained at the carbon monoxide pressures of 35 to 70 atm. Other chromium salts may be used with carbon monoxide and Grignard reagent in the preparation. The compound may also be obtained by the reaction of a chromium salt with carbon monoxide in the presence of magnesium in ether or sodium in diglyme.

General Description

White crystalline or granular solid. Sublimes at room temperature. Burns with a luminous flame.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Chromium hexacarbonyl decomposes violently at 410° F. Chromium hexacarbonyl is decomposed by chlorine and fuming nitric acid. Chromium hexacarbonyl is incompatible with oxidizing agents.

Hazard

Toxic by inhalation and ingestion.

Health Hazard

Chromium hexacarbonyl is a highly toxicsubstance by all routes of exposure. The toxiceffects are similar to those of molybdenumand tungsten carbonyls. The symptoms areheadache, dizziness, nausea, vomiting, andfever. The oral LD50 in mice is 150 mg/kgand in rats 230 mg/kg. The intravenous LD50in mice is 30 mg/kg. As a hexavalent compoundof chromium, it is a carcinogenic substance.

Fire Hazard

Flash point data for Chromium hexacarbonyl are not available; however, Chromium hexacarbonyl is probably combustible.

Potential Exposure

Chromium carbonyl is used as a catalyst for hydrogenation, isomerization, water
gas shift reaction and alkylation of aromatic hydrocarbons; gasoline additive to increase octane number; preparation of chromous oxide, CrO

Shipping

UN3466 Metal carbonyls, solid n.o.s. Hazard class 6.1. Technical name required. UN3281 Metal carbonyls, liquid n.o.s. Hazard class 6.1. Technical name required, Potential Inhalation Hazard (Special Provision 5). UN3466 Metal carbonyls, solid n.o.s. Hazard class 6.1. Technical name required.

Purification Methods

Wash the complex with cold EtOH, then Et2O, and allow it to dry in air. Alternatively recrystallise it from dry Et2O. This is best accomplished by placing the hexacarbonyl in a Soxhlet extractor and extracting exhaustively with dry Et2O. Pure Cr(CO)6 is filtered off and dried in air. Completely colourless refracting crystals are obtained by sublimation at 40-50o/<0.5mm in an apparatus where the collecting finger is cooled by Dry Ice and in which there is a wide short bore between the hot and cold sections to prevent clogging by the crystals. Loss of product in the crystallisation and sublimation is slight. It is important not to overdo the drying as the solid is appreciably volatile and TOXIC [vapour pressure is 0.04(8o), 1.0(48o) and 66.5(100o) mm]. Also do not allow the Et2O solutions to stand too long as a brown deposit is formed which is sensitive to light, and to avoid the possibility of violent decomposition. It sinters at 90o, decomposes at 130o, and EXPLODES at 210o. [Owen et al. Inorg Synth III 156 1950, Podall et al. J Am Chem Soc 83 2057 1961.] POISONOUS.

Incompatibilities

Violent reaction on contact with oxidizers. Decomposed by chlorine and fuming nitric acid; sensitive to heat and light (undergoes photochemical decomposition). Many carbonyls react with water, forming toxic and flammable vapors

Waste Disposal

Use a licensed professional waste disposal service to dispose of this material. All federal, state, and local environmental regulations must be observed. Consult with environmental regulatory agencies for guidance on acceptable disposal practices. Generators of waste containing this contaminant (>=100 kg/mo) must conform to EPA regulations governing storage, transportation, treatment, and waste disposal.

InChI:InChI=1/6CO.Cr/c6*1-2;/rC6CrO6/c8-1-7(2-9,3-10,4-11,5-12)6-13

Synthetic route

chromium(0) hexacarbonyl (199620-14-9, 13007-92-6) → chromium(CO)5(propanol) (13007-92-6)

Conditions	Yield
In propan-1-ol Irradiation (UV/VIS); laser-puls irradiation (308 nm, 90 fs, 400 nJ); not isolated; UV/VIS monitoring;

Upstream product

• 201230-82-2 carbon monoxide 
• 628-52-4 chromium(II) acetate 
• 7788-97-8 chromium(III) fluoride 
• 16065-83-1 chromium (III) ion 
• 7440-47-3 chromium 
• 51868-81-6 {Cr(Pyr)3Cl₃} 
• 10025-73-7 chromium(III) chloride 
• 27303-69-1 Tri-?-allyl-chrom 
• 14977-61-8 chromyl chloride 
• 12146-36-0 tetracarbonylnorbornadienchrom 

Downstream Products

• 34898-74-3 (Z)-α,α'-dimethoxystilbene 
• 22611-72-9 trans-α,α-dimethoxystilbene 
• 12129-27-0 (η6-p-xylene)tricarbonylchromium(0) 
• 41354-64-7 tricarbonyl(3-8-η-{2.2}paracyclophane)chromium 
• 16743-46-7 tetracarbonyl-bis(diphenylphosphino)methane-chromium(0) 
• 135760-63-3 Cr(CO)5(ClSiH(C₆H₅)2) 
• 18898-57-2 chromium(III) diethyldithiocarbamate 
• 56110-59-9 chromium tetracarbonyl 
• 22400-26-6 isocyanate radical 
• 26319-33-5 pentacarbonylchromium⁽⁰⁾ 
• 15603-93-7 Cr(CO)5[P(C₆H₁₁)3] 
• 24465-76-7 (CO)4Cr(PF₃)2 
• 697302-50-4 (benzene)tricarbonylchromium 
• 14917-12-5 triphenylphosphine chromium pentacarbonyl 

Related news

Infrared studies of the interaction of Chromium hexacarbonyl (cas 13007-92-6) and molybdenum hexacarbonyl with high-surface-area spinel09/04/2019

Infrared spectrometry was used to characterize the surface adducts formed on interaction of Cr(CO)6 and Mo(CO)6 with partially hydroxylated MgAl2O4 (spinel) prepared in a high-surface-area form. Cr(CO)6 is molecularly adsorbed and gives four characteristic IR absorption bands at 1890 cm-1 (O-bon...detailed

Surface Science LettersThe adsorption and decomposition of Chromium hexacarbonyl (cas 13007-92-6) on Pd(100)09/02/2019

Chromium hexacarbonyl [Cr(CO)6] was physisorbed on the Pd(100) surface, and the molecular orientation was determined using reflection-absorption infrared spectroscopy (RAIRS). The thermal decomposition of the compound was observed, by the indirect observation of a modified surface morphology, wh...detailed

Plasma enhanced chemical vapor deposition of Cr2O3 thin films using Chromium hexacarbonyl (cas 13007-92-6) (Cr(CO)6) precursor08/31/2019

Chromium oxide (Cr2O3) thin films have been deposited by plasma enhanced chemical vapor deposition on c-cut sapphire (Al2O3) and oxidized silicon substrates at temperatures between 250 and 400 °C using the precursor chromium hexacarbonyl (Cr(CO)6). The film growth rate ranges between 5 and 14 Å...detailed

Deposition of Chromium hexacarbonyl (cas 13007-92-6) on alumina in a fluidized bed reactor08/30/2019

Cr(CO)6/Al2O3 samples were prepared in a fluidized bed reactor by vapour phase adsorption of chromium hexacarbonyl under nitrogen flow. The preparation of the samples were followed by diffuse reflectance IR spectroscopy and the chromium content was determined by EDXRF. Deposition and pulse techn...detailed

Controlled deposition of Chromium hexacarbonyl (cas 13007-92-6) on silica surfaces in a fluidised bed reactor08/29/2019

Cr(CO)6/silica samples were prepared in a fluidised bed reactor by vapor phase adsorption of zerovalent chromium hexacarbonyl under N2 flow. Two different preparation methods were used; a vaporisation method without decarbonylation step and a pulse method in which a sample was decarbonylated aft...detailed

Relevant academic research and scientific papers

Chromium-manganese selenide carbonyl complexes: Paramagnetic clusters and relevance to C = O activation of acetone

The paramagnetic even-electron cluster, [Et4N] 2[Se2Cr3(CO)10], was found to react readily with Mn(CO)5Br in acetone to produce two unprecedented mixed chromium-manganese selenide carbonyl complexes, [Et4N][Me 2CSe2{Mn(CO)4}{Cr(CO)5} 2] ([Et4N][1]) and [Et4N]2[Se 2Mn3(CO)10{Cr(CO)5}2] ([Et4N]2[2]). X-ray crystallographic analysis showed that anion 1 consisted of two Se-Cr(CO)5 moieties, which were further bridged by one isopropylene group and one Mn(CO)4 moiety. The dianionic cluster 2 was shown to display a Se2Mn3 square-pyramidal core with each Se atom externally coordinated by one Cr(CO)5 group. The formation of complex 1, presumably via C=O activation of acetone, was further facilitated by acidification of the reaction of [Et4N]2[Se2Cr3(CO)10] with Mn(CO)5Br in acetone. Complex 1 readily transformed into 2 upon treatment with Mn2(CO)10 in a KOH/MeOH/MeCN solution. Cluster 2 was a 51-electron species, which readily converted to the known 49-electron cluster [Se2Mn3(CO)9]2- upon heating and bubbling with CO. Magnetic studies of the even-electron cluster, [Et4N]2[Se2Cr3(CO) 10], and the odd-electron species, [Et4N]2[2] and [PPN]2[Se2Mn3(CO)9], were determined by the SQUID measurement to have 2, 3, and 1 unpaired electrons, respectively. In addition, the nature and formation of complexes 1 and 2 are discussed, and the magnetic properties and electrochemistry of [Se 2Cr3(CO)10]2-, 2, and [Se 2Mn3(CO)9]2- were further studied and elucidated by molecular orbital calculations at the PW91 level of density functional theory.

Elementary Arrhenius Parameters in the CO-for-Ethylene Dissociative Substitution of Cr(CO)5(C2H4)

Gas-phase samples of Cr(CO)5(C2H4) are prepared in situ by laser irradiation of quantitative mixtures of Cr(CO)6, CO, and C2H4.In the presence of CO and C2H4, Cr(CO)5(C2H4) decays thermally to re-form Cr(CO)6 by the mechanism of dissociative substitution.Systematic study of the rate of this reaction as a function of partial pressures of CO and C2H4 yields the elementary high-pressure limiting thermal rate constant for unimolecular dissociation of Cr(CO)5(C2H4) (k1) and the relative constant for recombination of Cr(CO)5 with CO and C2H4 (k2/k3).Measurements of k1 and k2/k3 extended over a range of precisely controlled temperatures determine Arrhenius parameters reflecting energetic and statistical properties of these elementary rate processes.

Siliciumhaltige Carben-Komplexe IX. Thermische Fragmentierung von Alkoxy(triphenylsilyl)carben-Komplexen, (CO)5MC(OR)SiPh3 (M=Cr, Mo, W)

On thermolysis of (CO)3M=C(OEt)SiPh3 (M=W, Mo, Cr) in the solid state or in solution three different decomposition pathways are observed, which are unusual for Fischer-type carbene complexes; fragmentation of the complex to give triphenylsilane, ethylene

The Photochemical Synthesis of in Solution: I.r. Evidence for Co-ordinated Molecular Dihydrogen

(1) is synthesised by u.v. photolysis of dissolved in liquid Xe doped with H2 at 200 K and the co-ordinated molecular dihydrogen has a νH-H i.r. band at 3030 cm-1; can also be generated photochemically in n-heptane at room temperature under high pressures (100 atm) of H2.

Synthesis, structure, and reactivity of cyclic (arene)chromium carbene complexes

In contrast to benzannulation products obtained by photolysis, thermolysis of the chromium carbene complexes [(1,1′-biphenyl-2-yl)methoxymethylene]pentacarbonylchromium (1) and [(1,1′-biphenyl-2-yl)(dimethylamino)methylene]pentacarbonylchromium (4) provide the new cyclic arene carbene complexes {[(1′,2′,3′,4′,5′,6′-η)-1,1′- biphenyl-2-yl]methoxymethylene}dicarbonylchromium (3) and {[(1′,2′,3′,4′,5′,6′-η)-1,1′- biphenyl-2-yl](dimethylamino)methylene}dicarbonylchromium (5). The 13C NMR spectra of these new complexes have unusually high-field-shifted and low-field-shifted signals for the carbene and carbonyl carbon resonances, respectively. The complexes are remarkably stable and do not show the high electrophilic behavior typical of Fischer carbene complexes. A new protocol for the aminolysis of Fischer carbene complexes is reported. The structure of complexes 3 and 5 were determined by single-crystal X-ray diffraction studies. 3 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 16.154 (2) A?, b = 12.256 (2) A?, c = 15.575 (2) A?, and β = 122.92 (1)°, with Z = 8. 5 crystallizes in the monoclinic space group P21/n with unit cell dimensions a = 11.47 (1) A?, b = 7.082 (7) A?, c = 20.87 (2) A?, and β = 108.13 (2)°, with Z = 4. The structures were refined by full-matrix least-squares procedures to final R = 0.028 and Rw = 0.050 for 2074 unique observed reflections for 3 and R = 0.066 and Rw = 0.101 for 1580 unique observed reflections for 5.

Time-Resolved IR Study of Gas-Phase Reaction of Benzene with Group VIB Metal Pentacarbonyls and Tetracarbonyls

The gas-phase reactions of benzene and deuterated benzene (benzene-d6) with group VIB metal pentacarbonyls M(CO)5 (M=Cr and W) and tetracarbonyl W(CO)4 were probed with time-resolved infrared spectroscopy.Benzene reacts with M(CO)5 forming presumably (η2-benzene)M(CO)5 in which benzene coordinates to the metal via an isolated double bond.The rate constants for reactions of C6H6 and C6D6 with Cr(CO)5 were found to be (3.0 +/- 0.7) and (3.3 +/- 0.2) x 1013 cm3 mol-1 s-1, respectively.The corresponding values with W(CO)5 are (2.8 +/- 0.4) and (3.5 +/- 0.6) x 1013 cm3 mol-1 s-1.From the temperature dependence of the rate of dissociative loss of benzene from (η2-benzene)Cr(CO)5, a bond dissociation energy of 9.2 +/- 0.8 kcal mol-1 was determined for (η2-benzene)Cr(CO)5.The lower limit for bond dissociation energy for loss of the benzene ligand from (η2-benzene)W(CO)5 was estimated to be 11.7 kcal mol-1.Benzene reacts with W(CO)4 producing a species, presumably (η2-benzene)W(CO)4, which is stable in the milisecond time scale.The rate constants for reactions of C6H6 and C6D6 with W(CO)4 were determined to be (3.5 +/- 0.2) and (4.1 +/- 0.4) x 1013 cm3 mol-1 s-1, respectively.Secondary addition of CO to (η2-benzene)W(CO)4 forms (η2-benzene)W(CO)5, and the rate constants are (9.4 +/- 0.9) and (8.7 +/- 1.0) x 1011 cm3 mol-1 s-1, respectively, for additions of CO to (η2-C6H6)W(CO)4 and (η2-C6D6)W(CO)4.

STUDY OF THE PHOTOLYSIS OF ARENETRICARBONYLCHROMIUM COMPLEXES BY IR, UV AND 1H AND 13C NMR SPECTROSCOPY

The mechanism of photolysis of arenetricarbonylchromium complexes is investigated by a number of spectral techniques.Experimental data are obtained in favour of the formation during the ArCr(CO)3 photolysis of a multicenter complex, photodecay of which leads to the formation of chromium hexacarbonyl.A mechanism for the photolysis of arenetricarbonylchromium complexes is proposed.

Matrix isolation study into the mechanism of photoinduced cyclization reactions of chromium carbenes

The complex (CO)5Cr[C(OMe)(Me)] is known to react photochemically with N-benzyli-denemethylamine (CH3NC(Ph)H) to form a β-lactam (1,3-dimethyl-3-methoxy-4-phenyl-2-azetidinone), whereas our study shows that (CO)5W[C(OMe)(Me)] does not. Irradiation of the complexes in argon and nitrogen matrices (λ > 390 nm) resulted in a geometrical isomerization and the trapping of the syn isomers. There was no evidence from the matrix isolation experiments for the formation of a metal-ketene complex, a likely intermediate in the solution photochemistry of (CO)5Cr[C(OMe)(Me)] with respect to β-lactam formation. Three differences were observed in the matrix and solution photochemistry of (CO)5Cr-[C(OMe)(Me)] and (CO)5W[C(OMe)(Me)]. (i) (CO)5Cr[C(OMe)(Me)] undergoes CO loss upon irradiation with UV light more readily than its tungsten analogue, (ii) Upon UV irradiation of (CO)5Cr[(C(OMe)(Me)] in a nitrogen matrix bands were observed in the IR spectrum which indicated that two (CO)4(N2)Cr[C(OMe)(Me)] isomers were formed, whereas irradiation of (CO)5W[C(OMe)(Me)] under the same conditions produced only one nitrogen adduct. (iii) Irradiation of (CO)5Cr[C(OMe)(Me)] in solution and in a solid CO matrix showed that this complex underwent loss of the carbene ligand more readily than the tungsten analogue. These findings are consistent with the proposal that, upon irradiation of chromium carbenes, a ketene transient could be formed by a cleavage of the chromium-carbene σ bond and intramolecular nucleophilic attack by the carbene on a metal carbonyl. The photochemistry of the complex (CO)5Cr(OMeXbiphenyl) was studied in both argon and nitrogen matrices. This complex underwent CO loss very readily, and it is likely that this step is involved in at least one pathway of its solution photochemistry.

tBu2Si=Cr(CO)5 * Na(CF3SO3) * 2 THF: a salt-adduct of a chromium-silicon double bond

The salt-adduct (tBu)2Si=Cr(CO)5 * Na(CF3SO3) * 2 THF a chromium-silicon double bond has been investigated in the solid state and in solution.The triflate Na(CF3SO3) does not coordinate rigidly to 1 but exchanges rapidly in non-polar solvents (29Si-NMR 150.7 ppm).The X-ray crystal structure of 1*Na(CF3SO3) shows a Cr-Si bond distance of 2.475(1) Angstroem and an Si-O6 bond distance of 1.857(3) Angstroem.The sum of bond angles at Si is 349.5o.In the crystal the molecules of 1*Na(CF3SO3) are linked by heptacoordinate sodium ions to form a helix along the 21 direction of the unit cell (P21/c).Upon treatment with pyridine or CO, 1*Na(CF3SO3) eliminates di(tert-butyl)silylene which trimerizes to give cyclic 3. 1*Na(CF3SO3) can be transformed with HPMA (hexamethylphosphorotriamide) into (t-Bu)2(HMPA)Si=Cr(CO)5, 3.A single crystal X-ray structure determination of 3 shows a Cr-Si bond distance of 2.527(3) Angstroem and an Si-O6 bond distance of 1.777(6) Angstroem.Complex 3 can be described as a ?-donor complex (t-Bu)2(HMPA)Si -> Cr(CO)5.

Photoinduced Se-C insertion following photolysis of (η5- C4H4Se)Cr(CO)3. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation

The photochemistry of (η5;-C4H 4Se)Cr(CO)3 was investigated by matrix isolation, time-resolved infrared spectroscopy, and steady-state photochemical methods. Density functional theory (DFT) was used to assist in the identification of the photoproducts. Irradiation (λexc= 406 nm) of (η5-C4H4Se)Cr(CO)3 in either an Ar or CH4 matrix at 20 K produced the selenophene ring-opened insertion product (C,Se-C4H4Se)Cr(CO)3. Further irradiation of this matrix produced the CO-loss species (C,Se-C 4H4Se)Cr(CO)2. Pulsed irradiation at 400 nm produced the CO-loss species (η5-C4H 4Se)Cr(CO)2(S) in n-heptane (S) along with the insertion products (C,Se-C4H4Se)Cr(CO)3 and (C,Se-C 4H4Se)Cr(CO)2, both of which may have triplet character. Time-resolved measurements on the microsecond time scale confirmed that the CO-loss species (η5-C4H4Se)Cr(CO) 2(S) reacts with CO (k2 = 5.8 × 106 dm3 mol-1 s-1 at 298 K), while (C,Se-C4H 4Se)Cr(CO)3 and (C,Se-C4H4Se)Cr(CO) 2 do not react on this time scale. DFT calculations provide an explanation of the stability of the triplet (C,Se-C4H 4Se)Cr(CO)3 species in terms of a chromaselanabenzene structure, which is consistent with previously observed metal insertion into coordinated selenophene ligands.