Monomanganese, pentacarbonyl-

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 by: José A. Martinho Simões

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Individual Reactions

Hydromanganese pentacarbonyl (solution) = Hydrogen atom (solution) + C5MnO5 (solution)

By formula: C5HMnO5 (solution) = H (solution) + C5MnO5 (solution)

Quantity Value Units Method Reference Comment
ΔrH°68.0 ± 1.0kcal/molEChemParker, Handoo, et al., 1991solvent: Acetonitrile; Please also see Tilset and Parker, 1989. The reaction enthalpy was obtained from the pKa of the hydride complex (MH), 14.1, and from the oxidation potential of the anion (M-), Mn(CO)5(-), by using the equation: ΔHrxn [kJ/mol] = 5.71pKa(MH) + 96.485(Eo)ox(M-) + C. C is a constant that was calculated as 59.49 kcal/mol Parker, Handoo, et al., 1991, by adjusting the previous equation to the calorimetrically derived values for the reactions Cr(Cp)(CO)3(H)(solution) = Cr(Cp)(CO)3(solution) + H(solution), 61.5 ± 1.0 kcal/mol, and Cr(Cp)(CO)2(PPh3)(H)(solution) = Cr(Cp)(CO)2(PPh3)(solution) + H(solution), 59.8 ± 1.0 kcal/mol Kiss, Zhang, et al., 1990. C depends on the solvent and on the reference electrode. The value given implies that the electrode potentials are referenced to ferrocene/ferricinium electrode
ΔrH°64.46kcal/molKinSBillmers, Griffith, et al., 1986solvent: Benzene; Please also see Sweany, Butler S.C., et al., 1981. The reaction enthalpy was derived according to the following procedure: the activation energy for the reaction 9,10-Me2C14H8(solution) + 2Mn(CO)5(H)(solution) = 9,10-Me2C14H10(solution) + Mn2(CO)10(solution), 21.7 kcal/mol, was reported in Sweany, Butler S.C., et al., 1981. The rate-limiting step of this reaction is the abstraction of hydrogen from Mn(CO)5(H), producing Mn(CO)5 and 9,10-Me2C14H9 radicals. Therefore, the activation energy is approximately equal to the difference between the enthalpies of the reactions Mn(CO)5(H)(solution) = Mn(CO)5(solution) + H(solution) and 9,10-Me2C14H9(solution) = 9,10-Me2C14H8(solution). The latter was taken as 42.76 kcal/mol Billmers, Griffith, et al., 1986

Dimanganese decacarbonyl (solution) = 2C5MnO5 (solution)

By formula: C10Mn2O10 (solution) = 2C5MnO5 (solution)

Quantity Value Units Method Reference Comment
ΔrH°37.7 ± 4.1kcal/molES/EChemPugh and Meyer T.J., 1992solvent: Acetonitrile; The value relies on the reaction Gibbs energy, 28.1 ± 4.0 kcal/mol Pugh and Meyer T.J., 1992, and an estimated value, 133.9 J/(mol K), for the reaction entropy Pugh and Meyer T.J., 1992
ΔrH°>24.90kcal/molES/EChemPugh and Meyer, 1988solvent: Acetonitrile; The lower limit is the reaction Gibbs energy
ΔrH°38.0 ± 5.0kcal/molPACGoodman, Peters, et al., 1986solvent: Hexane, cyclohexane, thf or acetonitrile; The average value of the enthalpy of the reaction Mn2(CO)10(solution) = 2xMn(CO)5(solution) + (1-x)Mn2(CO)9(solution) + (1-x)CO(solution) in the solvents indicated is 12.8 ± 1.2 kcal/mol. This value, together with several estimates and auxiliary data led to the reaction enthalpy for the cleavage of Mn-Mn bond
ΔrH°>36.8kcal/molKinSHopgood and Poë, 1966solvent: Decalin; Please also see Poë, 1981. The reaction enthalpy was derived from the enthalpy of activation, 36.76 ± 0.38 kcal/mol Hopgood and Poë, 1966 Poë, 1981, by assuming a negligible barrier for the radical recombination. This procedure was later considered to yield a low limit of the reaction enthalpy Poë, 1983 Marcomini and Poë, 1984 Marcomini and Poë, 1983 Coville, Stolzenberg, et al., 1983. See also Schmidt, Trogler, et al., 1984

C12H7MnO5 (g) = C5MnO5 (g) + Benzyl radical (g)

By formula: C12H7MnO5 (g) = C5MnO5 (g) + C7H7 (g)

Quantity Value Units Method Reference Comment
ΔrH°32.3 ± 4.5kcal/molICR/PESMartinho Simões, Schultz, et al., 1985Please also see Martinho Simões and Beauchamp, 1990. The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 198.3 ± 4.6 kcal/mol, using Mn(CO)5(Bz) as the neutral precursor, together with the adiabatic ionization energy of Bz radical, 166.0 ± 0.45 kcal/mol Martinho Simões, Schultz, et al., 1985. The enthalpy of formation relies on -153.6 ± 2.2 kcal/mol for the enthalpy of formation of Mn(CO)5(Bz)(g)

Dimanganese decacarbonyl (g) = 2C5MnO5 (g)

By formula: C10Mn2O10 (g) = 2C5MnO5 (g)

Quantity Value Units Method Reference Comment
ΔrH°>42.1kcal/molESTSmith, 1988 
ΔrH°22.kcal/molESTConnor, Zafarani-Moattar, et al., 1982 
ΔrH°23. ± 3.1kcal/molEG/EIMSBidinosti and McIntyre, 1970The reaction enthalpy includes an estimated correction to 298 K. A value of 24.9 ± 2.0 kcal/mol was reported at an average temperature of 540 K Bidinosti and McIntyre, 1970. The enthalpy of formation relies on -378.9 ± 1.0 kcal/mol for the enthalpy of formation of Mn2(CO)10(g)

C6H2FMnO5 (g) = C5MnO5 (g) + Fluoromethyl radical (g)

By formula: C6H2FMnO5 (g) = C5MnO5 (g) + CH2F (g)

Quantity Value Units Method Reference Comment
ΔrH°33.2 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 212.2 ± 1.1 kcal/mol, using Mn(CO)5(CH2F) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

C6HF2MnO5 (g) = C5MnO5 (g) + Difluoromethyl radical (g)

By formula: C6HF2MnO5 (g) = C5MnO5 (g) + CHF2 (g)

Quantity Value Units Method Reference Comment
ΔrH°34.4 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 213.3 ± 1.1 kcal/mol, using Mn(CO)5(CHF2) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

C6F3MnO5 (g) = C5MnO5 (g) + Trifluoromethyl radical (g)

By formula: C6F3MnO5 (g) = C5MnO5 (g) + CF3 (g)

Quantity Value Units Method Reference Comment
ΔrH°43.5 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 222.5 ± 1.1 kcal/mol, using Mn(CO)5(CF3) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

Hydromanganese pentacarbonyl (g) = Hydrogen atom (g) + C5MnO5 (g)

By formula: C5HMnO5 (g) = H (g) + C5MnO5 (g)

Quantity Value Units Method Reference Comment
ΔrH°58.6 ± 4.1kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 237.5 ± 2.3 kcal/mol, using Mn(CO)5(H) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

Manganese, pentacarbonylmethyl- (g) = C5MnO5 (g) + Methane (g)

By formula: C6H3MnO5 (g) = C5MnO5 (g) + CH4 (g)

Quantity Value Units Method Reference Comment
ΔrH°45.9 ± 3.6kcal/molPIMSMartinho Simões and Beauchamp, 1990The reaction enthalpy was derived from the appearance energy of Mn(CO)5(+), 224.8 ± 1.1 kcal/mol, using Mn(CO)5(Me) as the neutral precursor, together with the adiabatic ionization energy of Mn(CO)5 radical, 179. ± 3.3 kcal/mol Martinho Simões and Beauchamp, 1990

References

Go To: Top, Reaction thermochemistry data, Notes

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

Parker, Handoo, et al., 1991
Parker, V.D.; Handoo, K.L.; Roness, F.; Tilset, M., J. Am. Chem. Soc., 1991, 113, 7493. [all data]

Tilset and Parker, 1989
Tilset, M.; Parker, V.D., J. Am. Chem. Soc., 1989, 111, 6711; ibid. 1990. [all data]

Kiss, Zhang, et al., 1990
Kiss, G.; Zhang, K.; Mukerjee, S.L.; Hoff, C.; Roper, G.C., J. Am. Chem. Soc., 1990, 112, 5657. [all data]

Billmers, Griffith, et al., 1986
Billmers, R.; Griffith, L.L.; Stein, S.E., J. Phys. Chem., 1986, 90, 517. [all data]

Sweany, Butler S.C., et al., 1981
Sweany, R.; Butler S.C.; Halpern, J., J. Organometal. Chem., 1981, 213, 487. [all data]

Pugh and Meyer T.J., 1992
Pugh, J.R.; Meyer T.J., J. Am. Chem. Soc., 1992, 114, 3784. [all data]

Pugh and Meyer, 1988
Pugh, J.R.; Meyer, T.J., J. Am. Chem. Soc., 1988, 110, 8245. [all data]

Goodman, Peters, et al., 1986
Goodman, J.L.; Peters, K.S.; Vaida, V., Organometallics, 1986, 5, 815. [all data]

Hopgood and Poë, 1966
Hopgood, D.; Poë, A.J., J. Chem. Soc., Chem. Commun., 1966, 831.. [all data]

Poë, 1981
Poë, A., ACS Symp. Ser., 1981, No. 155, 135. [all data]

Poë, 1983
Poë, A., Chem. Brit., 1983, 19, 997. [all data]

Marcomini and Poë, 1984
Marcomini, A.; Poë, A., J. Chem. Soc., Dalton Trans., 1984, 95.. [all data]

Marcomini and Poë, 1983
Marcomini, A.; Poë, A., J. Am. Chem. Soc., 1983, 105, 6952. [all data]

Coville, Stolzenberg, et al., 1983
Coville, N.J.; Stolzenberg, A.M.; Muetterties, E.L., J. Am. Chem. Soc., 1983, 105, 2499. [all data]

Schmidt, Trogler, et al., 1984
Schmidt, S.P.; Trogler, W.C.; Basolo, F., J. Am. Chem. Soc., 1984, 106, 1308. [all data]

Martinho Simões, Schultz, et al., 1985
Martinho Simões, J.A.; Schultz, J.C.; Beauchamp, J.L., Organometallics, 1985, 4, 1238. [all data]

Martinho Simões and Beauchamp, 1990
Martinho Simões, J.A.; Beauchamp, J.L., Chem. Rev., 1990, 90, 629. [all data]

Smith, 1988
Smith, G.P., Polyhedron, 1988, 7, 1605. [all data]

Connor, Zafarani-Moattar, et al., 1982
Connor, J.A.; Zafarani-Moattar, M.T.; Bickerton, J.; El-Saied, N.I.; Suradi, S.; Carson, R.; Al Takkhin, G.; Skinner, H.A., Organomet., 1982, 1, 1166. [all data]

Bidinosti and McIntyre, 1970
Bidinosti, D.R.; McIntyre, N.S., Mass spectrometric study of the thermal decomposition of dimanganese decacarbonyl and dicobalt octacarbonyl, Can. J. Chem., 1970, 48, 593. [all data]

Notes

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