Tungsten hexacarbonyl


Gas phase thermochemistry data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled by: José A. Martinho Simões

Quantity Value Units Method Reference Comment
Δfgas-209.7 ± 0.72kcal/molReviewMartinho Simões 
Δfgas-211.5 ± 1.1kcal/molReviewMartinho Simões 
Δfgas-211.0 ± 0.60kcal/molReviewMartinho Simões 
Δfgas-211.3 ± 0.65kcal/molReviewMartinho SimõesSelected data. Average of the values in Barnes, Pilcher, et al., 1974
Δfgas-211. ± 0.7kcal/molReviewMartinho Simões 

Condensed phase thermochemistry data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled by: José A. Martinho Simões

Quantity Value Units Method Reference Comment
Δfsolid-228.0 ± 0.65kcal/molReviewMartinho Simões 
Δfsolid-229.8 ± 1.0kcal/molReviewMartinho Simões 
Δfsolid-229.3 ± 0.50kcal/molReviewMartinho Simões 
Δfsolid-229.5 ± 0.57kcal/molReviewMartinho SimõesSelected data. Average of the values in Barnes, Pilcher, et al., 1974
Δfsolid-229. ± 0.7kcal/molReviewMartinho Simões 
Quantity Value Units Method Reference Comment
Δcsolid-536.0 ± 1.0kcal/molCC-SBBarnes, Pilcher, et al., 1974Please also see Pedley and Rylance, 1977 and Tel'noi and Rabinovich, 1977.
Δcsolid-537.81 ± 0.60kcal/molCC-SBCotton, Fischer, et al., 1956Please also see Pedley and Rylance, 1977, Cox and Pilcher, 1970, and Tel'noi and Rabinovich, 1977.

Reaction thermochemistry data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data compiled as indicated in comments:
MS - José A. Martinho Simões
B - John E. Bartmess

Note: Please consider using the reaction search for this species. This page allows searching of all reactions involving this species. A general reaction search form is also available. Future versions of this site may rely on reaction search pages in place of the enumerated reaction displays seen below.

Individual Reactions

Tungsten hexacarbonyl (solution) = C5O5W (solution) + Carbon monoxide (solution)

By formula: C6O6W (solution) = C5O5W (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr39.9 ± 1.6kcal/molKinSGraham and Angelici, 1967solvent: Decalin; The reaction enthalpy and entropy were identified with the enthalpy and entropy of activation for the reaction of W(CO)6(solution) with PBu3(solution).; MS
Δr39.01kcal/molKinSWerner and Prinz, 1966solvent: n-Decane+cyclohexane mixture; The reaction enthalpy and entropy were identified with the enthalpy and entropy of activation for the reactions of W(CO)6(solution) with a phosphine and an amine. The results were quoted from Graham and Angelici, 1967.; MS

Tungsten hexacarbonyl (g) = C5O5W (g) + Carbon monoxide (g)

By formula: C6O6W (g) = C5O5W (g) + CO (g)

Quantity Value Units Method Reference Comment
Δr46.0 ± 3.0kcal/molLPHPLewis, Golden, et al., 1984The reaction enthalpy at 298 K relies on an activation energy of 44.50 kcal/mol and assumes a negligible activation barrier for product recombination. The enthalpy of formation relies on -211.3 ± 0.65 kcal/mol for the enthalpy of formation of W(CO)6(g); MS
Δr39.79kcal/molKinGCetini and Gambino, 1963Please also see Graham and Angelici, 1967. The reaction enthalpy and entropy were identified with the enthalpy and entropy of activation for the reaction of W(CO)6(g) with CO(g) Cetini and Gambino, 1963. The results were quoted from Graham and Angelici, 1967.; MS

Tungsten hexacarbonyl (cr) = 6Carbon monoxide (g) + tungsten (cr)

By formula: C6O6W (cr) = 6CO (g) + W (cr)

Quantity Value Units Method Reference Comment
Δr71.4 ± 1.1kcal/molTD-HFC, HAL-HFCAl-Takhin, Connor, et al., 1984The reaction enthalpy corresponds to the TD experiments and leads to -229.9 ± 1.1 kcal/mol for the enthalpy of formation. The value -960±3 was recommended by the authors Al-Takhin, Connor, et al., 1984. Other values for the enthalpy of sublimation have been reported: 17.5 ± 0.2 kcal/mol Adedeji, Brown, et al., 1975, 17.7 ± 1.0 kcal/mol Hieber and Romberg, 1935, 16.7 ± 1.0 kcal/mol Rezukhina and Shvyrev, 1952, and 18.9 ± 0.26 kcal/mol Daamen, Ernsting, et al., 1979 Boxhoorn, Ernsting, et al., 1980. See also Pilcher, Ware, et al., 1975; MS
Δr70.77 ± 0.43kcal/molTD-HZCBarnes, Pilcher, et al., 1974Please also see Pedley and Rylance, 1977 and Tel'noi and Rabinovich, 1977.; MS

Tungsten hexacarbonyl (cr) + 1,3-Diazine (l) = C10H5NO5W (cr) + Carbon monoxide (g)

By formula: C6O6W (cr) + C4H4N2 (l) = C10H5NO5W (cr) + CO (g)

Quantity Value Units Method Reference Comment
Δr8.27kcal/molN/ANakashima and Adamson, 1982The reaction enthalpy was calculated from the enthalpy of the reaction W(CO)6(solution) + py(solution) = W(CO)5(py)(solution) + CO(solution) in cyclohexane, 6.55 ± 0.69 kcal/mol, together with the enthalpies of solution of W(CO)6(cr), W(CO)5(py)(cr), and py(l), 35.7, 36.4, and 1.9 kcal/mol, respectively Nakashima and Adamson, 1982.; MS

C9H9N3O3W (cr) = 0.5Tungsten hexacarbonyl (g) + 0.5tungsten (cr) + 3Acetonitrile (g)

By formula: C9H9N3O3W (cr) = 0.5C6O6W (g) + 0.5W (cr) + 3C2H3N (g)

Quantity Value Units Method Reference Comment
Δr46.6kcal/molTD-HFCAdedeji, Connor, et al., 1978The value for the reaction enthalpy corresponds to the thermal decomposition experiments and leads to -99.2 kcal/mol for the enthalpy of formation of W(CO)3(MeCN)3(cr). The value -405.0±12.0 was recommended by the authors Adedeji, Connor, et al., 1978; MS

Tungsten hexacarbonyl (solution) + 1,3-Diazine (solution) = C10H5NO5W (solution) + Carbon monoxide (solution)

By formula: C6O6W (solution) + C4H4N2 (solution) = C10H5NO5W (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr6.55 ± 0.69kcal/molPCNakashima and Adamson, 1982solvent: Cyclohexane; MS
Δr5.95 ± 0.69kcal/molPCNakashima and Adamson, 1982solvent: Benzene; MS
Δr4.40 ± 0.1kcal/molPCNakashima and Adamson, 1982solvent: Tetrahydrofuran; MS

Tungsten hexacarbonyl (solution) + Heptane (solution) = C12H16O5W (solution) + Carbon monoxide (solution)

By formula: C6O6W (solution) + C7H16 (solution) = C12H16O5W (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr32.60 ± 0.41kcal/molPACMorse, Parker, et al., 1989solvent: Heptane; The reaction enthalpy relies on 0.72 for the quantum yield of CO dissociation; MS

Hydrogen anion + Tungsten hexacarbonyl = (Hydrogen anion • Tungsten hexacarbonyl)

By formula: H- + C6O6W = (H- • C6O6W)

Quantity Value Units Method Reference Comment
Δr44.0 ± 4.0kcal/molN/ALane and Squires, 1988gas phase; Hydride affinity between CH2=O and PhCH=O; B

C8H6N2O4W (cr) + 2Carbon monoxide (g) = Tungsten hexacarbonyl (g) + 2Acetonitrile (g)

By formula: C8H6N2O4W (cr) + 2CO (g) = C6O6W (g) + 2C2H3N (g)

Quantity Value Units Method Reference Comment
Δr17.3 ± 0.91kcal/molDSCBleijerveld and Vrieze, 1976Please also see Bleyerveld, Höhle, et al., 1975.; MS

C9H9N3O3W (cr) + 3Carbon monoxide (g) = Tungsten hexacarbonyl (g) + 3Acetonitrile (g)

By formula: C9H9N3O3W (cr) + 3CO (g) = C6O6W (g) + 3C2H3N (g)

Quantity Value Units Method Reference Comment
Δr17.4 ± 1.2kcal/molDSCBleijerveld and Vrieze, 1976Please also see Bleyerveld, Höhle, et al., 1975.; MS

C7H3NO5W (cr) + Carbon monoxide (g) = Tungsten hexacarbonyl (g) + Acetonitrile (g)

By formula: C7H3NO5W (cr) + CO (g) = C6O6W (g) + C2H3N (g)

Quantity Value Units Method Reference Comment
Δr16.9 ± 0.60kcal/molDSCBleijerveld and Vrieze, 1976Please also see Bleyerveld, Höhle, et al., 1975.; MS

Tetrahydrofuran (solution) + Tungsten hexacarbonyl (solution) = C9H8O6W (solution) + Carbon monoxide (solution)

By formula: C4H8O (solution) + C6O6W (solution) = C9H8O6W (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr14.5 ± 1.0kcal/molPCNakashima and Adamson, 1982solvent: Tetrahydrofuran; MS

C10H5NO5W (cr) + Carbon monoxide (g) = Tungsten hexacarbonyl (g) + 1,3-Diazine (g)

By formula: C10H5NO5W (cr) + CO (g) = C6O6W (g) + C4H4N2 (g)

Quantity Value Units Method Reference Comment
Δr20. ± 2.4kcal/molDSCDaamen, van der Poel, et al., 1979Please also see Meester, Vriends, et al., 1976.; MS

Tungsten hexacarbonyl (solution) + Acetone (solution) = C8H6O6W (solution) + Carbon monoxide (solution)

By formula: C6O6W (solution) + C3H6O (solution) = C8H6O6W (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr17.9 ± 1.4kcal/molPCNakashima and Adamson, 1982solvent: Acetone; MS

Tungsten hexacarbonyl (cr) + 31,3-Diazine (g) = C18H15N3O3W (g) + 3Carbon monoxide (g)

By formula: C6O6W (cr) + 3C4H4N2 (g) = C18H15N3O3W (g) + 3CO (g)

Quantity Value Units Method Reference Comment
Δr-13.1 ± 2.0kcal/molHFCAdedeji, Connor, et al., 1978MS

Tungsten hexacarbonyl (g) = C3O3W (g) + 3Carbon monoxide (g)

By formula: C6O6W (g) = C3O3W (g) + 3CO (g)

Quantity Value Units Method Reference Comment
Δr111. ± 10.kcal/molMBPSVenkataraman, Hou, et al., 1990MS

Gas phase ion energetics data

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Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Data evaluated as indicated in comments:
HL - Edward P. Hunter and Sharon G. Lias

Data compiled as indicated in comments:
LBLHLM - Sharon G. Lias, John E. Bartmess, Joel F. Liebman, John L. Holmes, Rhoda D. Levin, and W. Gary Mallard
LLK - Sharon G. Lias, Rhoda D. Levin, and Sherif A. Kafafi
RDSH - Henry M. Rosenstock, Keith Draxl, Bruce W. Steiner, and John T. Herron

Quantity Value Units Method Reference Comment
Proton affinity (review)181.2kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity175.3kcal/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
8.0PECooper, Green, et al., 1987LBLHLM
8.2PEHubbard and Lichtenberger, 1982LBLHLM
8.60 ± 0.02EIMichels, Flesch, et al., 1980LLK
8.242 ± 0.006PILloyd and Schlag, 1969RDSH
8.48 ± 0.05EIJunk and Svec, 1968RDSH
8.5 ± 0.1EIBidinosti and McIntyre, 1967RDSH
8.56 ± 0.13EIWinters and Kiser, 1965RDSH
8.46 ± 0.02EIFoffani, Pignataro, et al., 1965RDSH
8.18 ± 0.03PIVilesov and Kurbatov, 1961RDSH
8.59PEHubbard and Lichtenberger, 1982Vertical value; LBLHLM
8.56PEHead, Nixon, et al., 1975Vertical value; LLK
8.30 ± 0.02PEHigginson, Lloyd, et al., 1973Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
COW+18.36 ± 0.065COEIMichels, Flesch, et al., 1980LLK
COW+18.515COEIJunk and Svec, 1968RDSH
COW+18.7 ± 0.35COEIBidinosti and McIntyre, 1967RDSH
COW+20.2 ± 0.35COEIWinters and Kiser, 1965RDSH
COW+18.5 ± 0.165COEIFoffani, Pignataro, et al., 1965RDSH
WC+28.8 ± 0.5?EIWinters and Kiser, 1965RDSH
C2OW+25.9 ± 0.6?EIWinters and Kiser, 1965RDSH
C2O2W+16.29 ± 0.044COEIMichels, Flesch, et al., 1980LLK
C2O2W+16.084COEIJunk and Svec, 1968RDSH
C2O2W+15.8 ± 0.34COEIBidinosti and McIntyre, 1967RDSH
C2O2W+17.6 ± 0.24COEIWinters and Kiser, 1965RDSH
C2O2W+16.07 ± 0.044COEIFoffani, Pignataro, et al., 1965RDSH
C3O3W+14.06 ± 0.023COEIMichels, Flesch, et al., 1980LLK
C3O3W+13.873COEIJunk and Svec, 1968RDSH
C3O3W+13.70 ± 0.153COEIBidinosti and McIntyre, 1967RDSH
C3O3W+14.9 ± 0.23COEIWinters and Kiser, 1965RDSH
C3O3W+13.60 ± 0.023COEIFoffani, Pignataro, et al., 1965RDSH
C4O4W+12.22 ± 0.032COEIMichels, Flesch, et al., 1980LLK
C4O4W+12.052COEIJunk and Svec, 1968RDSH
C4O4W+11.93 ± 0.152COEIBidinosti and McIntyre, 1967RDSH
C4O4W+12.7 ± 0.22COEIWinters and Kiser, 1965RDSH
C4O4W+11.82 ± 0.022COEIFoffani, Pignataro, et al., 1965RDSH
C5O5W+10.30 ± 0.03COEIMichels, Flesch, et al., 1980LLK
C5O5W+~9.21COEIJunk and Svec, 1968RDSH
C5O5W+9.9 ± 0.1COEIBidinosti and McIntyre, 1967RDSH
C5O5W+9.80 ± 0.17COEIWinters and Kiser, 1965RDSH
C5O5W+9.97 ± 0.04COEIFoffani, Pignataro, et al., 1965RDSH
W+21.01 ± 0.056COEIMichels, Flesch, et al., 1980LLK
W+22.256COEIJunk and Svec, 1968RDSH
W+21.7 ± 0.36COEIBidinosti and McIntyre, 1967RDSH
W+22.9 ± 0.66COEIWinters and Kiser, 1965RDSH
W+20.6 ± 0.26COEIFoffani, Pignataro, et al., 1965RDSH

References

Go To: Top, Gas phase thermochemistry data, Condensed phase thermochemistry data, Reaction thermochemistry data, Gas phase ion energetics data, Notes

Data compilation copyright by the U.S. Secretary of Commerce on behalf of the U.S.A. All rights reserved.

Martinho Simões
Martinho Simões, J.A., Private communication (see http://webbook.nist.gov/chemistry/om/). [all data]

Barnes, Pilcher, et al., 1974
Barnes, D.S.; Pilcher, G.; Pittam, D.A.; Skinner, H.A.; Todd, D., J. Less-Common Met., 1974, 38, 53. [all data]

Pedley and Rylance, 1977
Pedley, J.B.; Rylance, J., Computer Analysed Thermochemical Data: Organic and Organometallic Compounds, University of Sussex, Brigton, 1977. [all data]

Tel'noi and Rabinovich, 1977
Tel'noi, V.I.; Rabinovich, I.B., Russ. Chem. Rev., 1977, 46, 689. [all data]

Cotton, Fischer, et al., 1956
Cotton, F.A.; Fischer, A.K.; Wilkinson. G., J. Am. Chem. Soc., 1956, 78, 5168. [all data]

Cox and Pilcher, 1970
Cox, J.D.; Pilcher, G., Thermochemistry of Organic and Organometallic Compounds in Academic Press, New York, 1970. [all data]

Graham and Angelici, 1967
Graham, J.R.; Angelici, R.J., Inorg. Chem., 1967, 6, 2082. [all data]

Werner and Prinz, 1966
Werner, H.; Prinz, R., Chem. Ber., 1966, 99, 3582. [all data]

Lewis, Golden, et al., 1984
Lewis, K.E.; Golden, D.M.; Smith, G.P., Organometallic bond dissociation energies: Laser pyrolysis of Fe(CO)5, Cr(CO)6, Mo(CO)6, and W(CO)6, J. Am. Chem. Soc., 1984, 106, 3905. [all data]

Cetini and Gambino, 1963
Cetini, G.; Gambino, O., Atti Accad. Sci. Torino, Classe Sci. Fis. Mat. Nat., 1963, 97, 1197. [all data]

Al-Takhin, Connor, et al., 1984
Al-Takhin, G.; Connor, J.A.; Pilcher, G.; Skinner, H.A., J. Organomet. Chem., 1984, 265, 263. [all data]

Adedeji, Brown, et al., 1975
Adedeji, F.A.; Brown, D.L.S.; Connor, J.A.; Leung, M.; Paz-Andrade, I.M.; Skinner, H.A., J. Organometal. Chem., 1975, 97, 221. [all data]

Hieber and Romberg, 1935
Hieber, W.; Romberg, E., Z. Anorg. Allg. Chem., 1935, 221, 321. [all data]

Rezukhina and Shvyrev, 1952
Rezukhina, T.N.; Shvyrev, V.V., Vestn. Moskov. Univ., 1952, 7, 41. [all data]

Daamen, Ernsting, et al., 1979
Daamen, H.; Ernsting, J.M.; Oskam, A., Thermochim. Acta, 1979, 33, 217. [all data]

Boxhoorn, Ernsting, et al., 1980
Boxhoorn, G.; Ernsting, J.M.; Stufkens, D.J.; Oskam, A., Thermochim. Acta, 1980, 42, 315. [all data]

Pilcher, Ware, et al., 1975
Pilcher, G.; Ware, M.J.; Pittam, D.A., J. Less-Common Met., 1975, 42, 223. [all data]

Nakashima and Adamson, 1982
Nakashima, M.; Adamson, A.W., J. Phys. Chem., 1982, 86, 2905. [all data]

Adedeji, Connor, et al., 1978
Adedeji, F.A.; Connor, J.A.; Demain, C.P.; Martinho Simões, J.A.; Skinner, H.A.; Zafarani- Moattar, M.T., J. Organometal. Chem., 1978, 149, 333. [all data]

Morse, Parker, et al., 1989
Morse, J.M., Jr.; Parker, G.H.; Burkey, T.J., Organometallics, 1989, 8, 2471. [all data]

Lane and Squires, 1988
Lane, K.R.; Squires, R.R., Hydride Transfer to Transition Metal Carbonyls in the Gas Phase. Formation and Relative Stabilities of Anionic Formyl Complexes, Polyhedron, 1988, 7, 16-17, 1609, https://doi.org/10.1016/S0277-5387(00)81786-6 . [all data]

Bleijerveld and Vrieze, 1976
Bleijerveld, R.H.T.; Vrieze, K., Inorg. Chim. Acta, 1976, 19, 195. [all data]

Bleyerveld, Höhle, et al., 1975
Bleyerveld, R.H.T.; Höhle, Th.; Vrieze, K., J. Organometal. Chem., 1975, 281, 284. [all data]

Daamen, van der Poel, et al., 1979
Daamen, H.; van der Poel, H.; Stufkens, D.J.; Oskam, A., Thermochim. Acta, 1979, 34, 69. [all data]

Meester, Vriends, et al., 1976
Meester, M.A.M.; Vriends, R.C.J.; Stufkens, D.J.; Vrieze, K., Inorg. Chim. Acta, 1976, 19, 95. [all data]

Venkataraman, Hou, et al., 1990
Venkataraman, B.; Hou, H.; Zhang, Z.; Chen, S.; Bandukwalla, G.; Vernon, M., J. Chem. Phys., 1990, 92, 5338. [all data]

Hunter and Lias, 1998
Hunter, E.P.; Lias, S.G., Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update, J. Phys. Chem. Ref. Data, 1998, 27, 3, 413-656, https://doi.org/10.1063/1.556018 . [all data]

Cooper, Green, et al., 1987
Cooper, G.; Green, J.C.; Payne, M.; Dobson, B.R.; Hillier, I.H., Photoelectron spectroscopy with variable photon energy: A study of the metal hexacarbonyls, M(CO)6, Where M = CR, MO, and W., J. Am. Chem. Soc., 1987, 109, 3836. [all data]

Hubbard and Lichtenberger, 1982
Hubbard, J.L.; Lichtenberger, D.L., Vibrational fine structure in the valence ionizations of transition-metal hexacarbonyls: New experimental indication of metal-to-carbonyl π bonding, J. Am. Chem. Soc., 1982, 104, 2132. [all data]

Michels, Flesch, et al., 1980
Michels, G.D.; Flesch, G.D.; Svec, H.J., Comparative mass spectrometry of the group 6B hexacarbonyls and pentacarbonyl thiocarbonyls, Inorg. Chem., 1980, 19, 479. [all data]

Lloyd and Schlag, 1969
Lloyd, D.R.; Schlag, E.W., Photoionization studies of metal carbonyls. I. Ionization potentials and the bonding in group VI metal hexacarbonyls and in mononuclear carbonyls and nitrosyl carbonyls of iron, cobalt, and nickel, Inorg. Chem., 1969, 8, 2544. [all data]

Junk and Svec, 1968
Junk, G.A.; Svec, H.J., Energetics of the ionization and dissociation of Ni(CO)4, Fe(CO)5, Cr(CO)6, Mo(CO)6 and W(CO)6, Z. Naturforsch., 1968, 23b, 1. [all data]

Bidinosti and McIntyre, 1967
Bidinosti, D.R.; McIntyre, N.S., Electron-impact study of some binary metal carbonyls, Can. J. Chem., 1967, 45, 641. [all data]

Winters and Kiser, 1965
Winters, R.E.; Kiser, R.W., Mass spectrometric studies of chromium, molybdenum, and tungsten hexacarbonyls, Inorg. Chem., 1965, 4, 157. [all data]

Foffani, Pignataro, et al., 1965
Foffani, A.; Pignataro, S.; Cantone, B.; Grasso, F., Mass spectra of metal hexacarbonyls, Z. Physik. Chem. (Frankfurt), 1965, 45, 79. [all data]

Vilesov and Kurbatov, 1961
Vilesov, F.I.; Kurbatov, B.L., Photoionization of esters and metal carbonyis in the gaseous phase, Dokl. Akad. Nauk SSSR, 1961, 140, 1364, In original 792. [all data]

Head, Nixon, et al., 1975
Head, R.A.; Nixon, J.F.; Sharp, G.J.; Clark, R.J., Photoelectron spectroscopic study of metal trifluorophosphine and hydridotrifluorophosphine complexes, J. Chem. Soc. Dalton Trans., 1975, 2054. [all data]

Higginson, Lloyd, et al., 1973
Higginson, B.R.; Lloyd, D.R.; Burroughs, P.; Gibson, D.M.; Orchard, A.F., Photoelectron studies of metal carbonyls. Part 2. The valence region photoelectron spectra of the Group VIA hexacarbonyls, J. Chem. Soc. Faraday Trans. 2, 1973, 1659. [all data]


Notes

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