Molybdenum hexacarbonyl

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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-234.8 ± 0.65kcal/molReviewMartinho Simões 
Δfsolid-229.5 ± 1.0kcal/molReviewMartinho Simões 
Δfsolid-236.6 ± 1.0kcal/molReviewMartinho Simões 
Δfsolid-236.4 ± 0.43kcal/molReviewMartinho SimõesSelected data.
Quantity Value Units Method Reference Comment
Δcsolid-505.7 ± 1.0kcal/molCC-SBBarnes, Pilcher, et al., 1974Please also see Pedley and Rylance, 1977 and Tel'noi and Rabinovich, 1977.
Δcsolid-507.50 ± 0.60kcal/molCC-SBCotton, Fischer, et al., 1956Please also see Pedley and Rylance, 1977, Cox and Pilcher, 1970, and Tel'noi and Rabinovich, 1977.

Phase change 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
AC - William E. Acree, Jr., James S. Chickos

Quantity Value Units Method Reference Comment
Δsub17.6 ± 0.24kcal/molCC-SBPilcher, Ware, et al., 1975Other values for the enthalpy of sublimation have been reported: 16.7 ± 1.0 kcal/mol Hieber and Romberg, 1935 Monchamp and Cotton, 1960, 17.3 ± 1.0 kcal/mol Rezukhina and Shvyrev, 1952, and 18.4 ± 0.2 kcal/mol Daamen, Ernsting, et al., 1979 Boxhoorn, Ernsting, et al., 1980; MS

Enthalpy of sublimation

ΔsubH (kcal/mol) Temperature (K) Method Reference Comment
18.6265. to 300.N/AOhta, Cicoira, et al., 2001AC
16.5331.AStephenson and Malanowski, 1987Based on data from 316. to 423. K.; AC
18.4 ± 0.2263.MEDaamen, Ernsting, et al., 1979, 2Based on data from 240. to 285. K. See also Boxhoorn, Ernsting, et al., 1980, 2.; AC
16.7363.N/AMonchamp and Cotton, 1960, 2Based on data from 343. to 383. K.; AC
17.3323. to 403.N/ARezukhina and Shvyrev, 1952AC
17.4292. to 308.N/ALander and Germer, 1947AC

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

Molybdenum hexacarbonyl (solution) = C5MoO5 (solution) + Carbon monoxide (solution)

By formula: C6MoO6 (solution) = C5MoO5 (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr31.7 ± 1.4kcal/molKinSGraham and Angelici, 1967solvent: Decalin; The reaction enthalpy and entropy were identified with the enthalpy and entropy of activation for the reaction of Mo(CO)6(solution) with PBu3(solution).; MS
Δr30.21kcal/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 Mo(CO)6(solution) with a phosphine and an amine. The results were quoted from Graham and Angelici, 1967.; MS

Molybdenum hexacarbonyl (g) = C5MoO5 (g) + Carbon monoxide (g)

By formula: C6MoO6 (g) = C5MoO5 (g) + CO (g)

Quantity Value Units Method Reference Comment
Δr34.9 ± 5.0kcal/molKinGGanske and Rosenfeld, 1990MS
Δr40.5 ± 3.0kcal/molLPHPLewis, Golden, et al., 1984The reaction enthalpy at 298 K relies on an activation energy of 39.01 kcal/mol and assumes a negligible activation barrier for product recombination. The enthalpy of formation relies on -218.8 ± 0.50 kcal/mol for the enthalpy of formation of Mo(CO)6(g); MS
Δr30.21kcal/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 Mo(CO)6(g) with CO(g) Cetini and Gambino, 1963. The results were quoted from Graham and Angelici, 1967.; MS

Molybdenum hexacarbonyl (solution) + Heptane (solution) = C12H16MoO5 (solution) + Carbon monoxide (solution)

By formula: C6MoO6 (solution) + C7H16 (solution) = C12H16MoO5 (solution) + CO (solution)

Quantity Value Units Method Reference Comment
Δr32.3 ± 2.9kcal/molPACJohnson, Popov, et al., 1991solvent: Heptane; The reaction enthalpy relies on 0.67 for the quantum yield of CO dissociation.; MS
Δr31.8 ± 1.3kcal/molPACMorse, Parker, et al., 1989solvent: Heptane; The reaction enthalpy relies on 0.67 for the quantum yield of CO dissociation; MS

Molybdenum hexacarbonyl (cr) = 6Carbon monoxide (g) + molybdenum (cr)

By formula: C6MoO6 (cr) = 6CO (g) + Mo (cr)

Quantity Value Units Method Reference Comment
Δr77.89 ± 0.36kcal/molTD-HZCBarnes, Pilcher, et al., 1974Please also see Pedley and Rylance, 1977 and Tel'noi and Rabinovich, 1977.; MS
Δr71.0 ± 1.0kcal/molTD-HFCConnor, Skinner, et al., 1972Please also see Pedley and Rylance, 1977 and Tel'noi and Rabinovich, 1977.; MS

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

By formula: H- + C6MoO6 = (H- • C6MoO6)

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

Molybdenum hexacarbonyl (cr) + 31,3-Diazine (g) = C18H15MoN3O3 (cr) + 3Carbon monoxide (g)

By formula: C6MoO6 (cr) + 3C4H4N2 (g) = C18H15MoN3O3 (cr) + 3CO (g)

Quantity Value Units Method Reference Comment
Δr-12.0 ± 1.7kcal/molHFCAdedeji, Connor, et al., 1978MS

C10H5MoNO5 (cr) + Carbon monoxide (g) = Molybdenum hexacarbonyl (g) + 1,3-Diazine (g)

By formula: C10H5MoNO5 (cr) + CO (g) = C6MoO6 (g) + C4H4N2 (g)

Quantity Value Units Method Reference Comment
Δr14. ± 0.7kcal/molDSCDaamen, van der Poel, et al., 1979MS

Molybdenum hexacarbonyl (g) = C3MoO3 (g) + 3Carbon monoxide (g)

By formula: C6MoO6 (g) = C3MoO3 (g) + 3CO (g)

Quantity Value Units Method Reference Comment
Δr105. ± 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)182.3kcal/molN/AHunter and Lias, 1998HL
Quantity Value Units Method Reference Comment
Gas basicity176.4kcal/molN/AHunter and Lias, 1998HL

Ionization energy determinations

IE (eV) Method Reference Comment
8.25PECooper, Green, et al., 1987LBLHLM
8.2PEHubbard and Lichtenberger, 1982LBLHLM
8.46 ± 0.01EIMichels, Flesch, et al., 1980LLK
8.50 ± 0.05EIPaetzold and Abd-el-Mottaleb, 1975LLK
8.227 ± 0.011PILloyd and Schlag, 1969RDSH
8.43 ± 0.05EIJunk and Svec, 1968RDSH
8.46 ± 0.08EIBidinosti and McIntyre, 1967RDSH
8.23 ± 0.12EIWinters and Kiser, 1965RDSH
8.30 ± 0.03EIFoffani, Pignataro, et al., 1965RDSH
8.12 ± 0.03PIVilesov and Kurbatov, 1961RDSH
8.45PEHubbard and Lichtenberger, 1982Vertical value; LBLHLM
8.50PEHead, Nixon, et al., 1975Vertical value; LLK
8.50 ± 0.02PEHigginson, Lloyd, et al., 1973Vertical value; LLK

Appearance energy determinations

Ion AE (eV) Other Products MethodReferenceComment
MoC+24. ± 1.?EIBidinosti and McIntyre, 1967RDSH
MoC+27.2 ± 0.4?EIWinters and Kiser, 1965RDSH
CMoO+16.52 ± 0.035COEIMichels, Flesch, et al., 1980LLK
MoCO+15.615COEIJunk and Svec, 1968RDSH
MoCO+15.7 ± 0.25COEIBidinosti and McIntyre, 1967RDSH
MoCO+18.1 ± 0.35COEIWinters and Kiser, 1965RDSH
MoCO+15.8 ± 0.065COEIFoffani, Pignataro, et al., 1965RDSH
C2MoO2+14.86 ± 0.024COEIMichels, Flesch, et al., 1980LLK
MoC2O2+14.764COEIJunk and Svec, 1968RDSH
MoC2O2+14.5 ± 0.14COEIBidinosti and McIntyre, 1967RDSH
MoC2O2+15.6 ± 0.34COEIWinters and Kiser, 1965RDSH
MoC2O2+13.9 ± 0.34COEIFoffani, Pignataro, et al., 1965RDSH
C3MoO3+13.29 ± 0.023COEIMichels, Flesch, et al., 1980LLK
MoC3O3+13.183COEIJunk and Svec, 1968RDSH
MoC3O3+12.8 ± 0.13COEIBidinosti and McIntyre, 1967RDSH
MOC3O3+13.7 ± 0.33COEIWinters and Kiser, 1965RDSH
MoC3O3+12.36 ± 0.123COEIFoffani, Pignataro, et al., 1965RDSH
C4MoO4+11.61 ± 0.022COEIMichels, Flesch, et al., 1980LLK
MoC4O4+10.722COEIJunk and Svec, 1968RDSH
MoC4O4+10.63 ± 0.152COEIBidinosti and McIntyre, 1967RDSH
MoC4O4+11.9 ± 0.22COEIWinters and Kiser, 1965RDSH
MoC4O4+11.28 ± 0.142COEIFoffani, Pignataro, et al., 1965RDSH
C5MoO5+10.02 ± 0.02COEIMichels, Flesch, et al., 1980LLK
MoC5O5+9.14COEIJunk and Svec, 1968RDSH
MoC5O5+9.4 ± 0.1COEIBidinosti and McIntyre, 1967RDSH
MoC5O5+9.80 ± 0.15COEIWinters and Kiser, 1965RDSH
MoC5O5+9.64 ± 0.05COEIFoffani, Pignataro, et al., 1965RDSH
Mo+18.24 ± 0.066COEIMichels, Flesch, et al., 1980LLK
Mo+19.636COEIJunk and Svec, 1968RDSH
Mo+18.6 ± 0.26COEIBidinosti and McIntyre, 1967RDSH
Mo+20.7 ± 0.56COEIWinters and Kiser, 1965RDSH
Mo+18.3 ± 0.36COEIFoffani, Pignataro, et al., 1965RDSH
MoO+24. ± 1.?EIBidinosti and McIntyre, 1967RDSH

Mass spectrum (electron ionization)

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

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

Data compiled by: NIST Mass Spectrometry Data Center, William E. Wallace, director

Spectrum

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Owner NIST Mass Spectrometry Data Center
Collection (C) 2014 copyright by the U.S. Secretary of Commerce
on behalf of the United States of America. All rights reserved.
Origin D.HENNEBERG, MAX-PLANCK INSTITUTE, MULHEIM, WEST GERMANY
NIST MS number 60913

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References

Go To: Top, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Mass spectrum (electron ionization), 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.; Virmani, Y., J. Less-Common Met., 1974, 36, 177. [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]

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

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

Monchamp and Cotton, 1960
Monchamp, R.R.; Cotton, F.A., J. Chem. Soc., 1960, 1438.. [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]

Ohta, Cicoira, et al., 2001
Ohta, T.; Cicoira, F.; Doppelt, P.; Beitone, L.; Hoffmann, P., Static Vapor Pressure Measurement of Low Volatility Precursors for Molecular Vapor Deposition Below Ambient Temperature, Chem. Vap. Deposition, 2001, 7, 1, 33-37, https://doi.org/10.1002/1521-3862(200101)7:1<33::AID-CVDE33>3.0.CO;2-Y . [all data]

Stephenson and Malanowski, 1987
Stephenson, Richard M.; Malanowski, Stanislaw, Handbook of the Thermodynamics of Organic Compounds, 1987, https://doi.org/10.1007/978-94-009-3173-2 . [all data]

Daamen, Ernsting, et al., 1979, 2
Daamen, H.; Ernsting, J.M.; Oskam, A., Vapour pressure measurements on M(CO)5L (M = Cr, Mo, W; L = piperidine, pyridine, pyrazine, pyrazole, thiazole), Thermochimica Acta, 1979, 33, 217-223, https://doi.org/10.1016/0040-6031(79)87044-6 . [all data]

Boxhoorn, Ernsting, et al., 1980, 2
Boxhoorn, G.; Ernsting, J.M.; Stufkens, D.J.; Oskam, A., Vapour pressure measurements on M(CO)5L complexes (M «58875» Cr, W; L «58875» CO, P(OØ)3, PØ3, PMe3, NMe3 and pyridazine), Thermochimica Acta, 1980, 42, 3, 315-321, https://doi.org/10.1016/0040-6031(80)85092-1 . [all data]

Monchamp and Cotton, 1960, 2
Monchamp, R.R.; Cotton, F.A., 289. Comparison of calorimetric and spectroscopic entropies of molybdenum hexacarbonyl, J. Chem. Soc., 1960, 1438, https://doi.org/10.1039/jr9600001438 . [all data]

Lander and Germer, 1947
Lander, J.J.; Germer, L.H., Metals Technology, Tech. Publ. 2259, 1947, 14, 6. [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]

Ganske and Rosenfeld, 1990
Ganske, J.A.; Rosenfeld, R.N., J. Phys. Chem., 1990, 94, 4315. [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, 757. [all data]

Johnson, Popov, et al., 1991
Johnson, F.P.A.; Popov, V.K.; George, M.W.; Bagratashvili, V.N.; Poliakoff, M.; Turner, J.J., Mendeleev Commun., 1991, 145.. [all data]

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

Connor, Skinner, et al., 1972
Connor, J.A.; Skinner, H.A.; Virmani, Y., Microcalorimetric studies. Thermal decomposition and iodination of metal carbonyls, J. Chem. Soc., Faraday Trans. 1, 1972, 68, 0, 1754, https://doi.org/10.1039/f19726801754 . [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]

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]

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]

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]

Paetzold and Abd-el-Mottaleb, 1975
Paetzold, R.; Abd-el-Mottaleb, S., Correlative studies of some spectroscopic and bonding parameters in octahedrally coordinated metal carbonyl complexes, J. Mol. Struct., 1975, 24, 357. [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

Go To: Top, Condensed phase thermochemistry data, Phase change data, Reaction thermochemistry data, Gas phase ion energetics data, Mass spectrum (electron ionization), References