20
K. Yoshizawa and M. Miyanishi
FeO(CH 4 )
+ in the gas-phase reaction. Recently, a similar distortion of methane is
discussed in the adsorption and activation of CH 4 on IrO 2 (110) surface, which
exactly involves five-coordinate Ir atoms [49]. We looked at mechanistic aspects
about methane hydroxylation by the bare transition-metal oxide ions such as FeO
+
based on DFT calculations. Detailed discussion on the reactivity of the first-row
transition-metal oxide ions from ScO
+ to CuO
+ is given in Chapter “Theoretical
Study of the Direct Conversion of Methane by First-Row Transition-Metal Oxide
Cations in the Gas Phase”. An important feature in the reaction is the spin crossover
between the high-spin and low-spin potential energy surfaces in particular in the
C–H activation process, the energy barrier of which is significantly decreased by the
spin inversion. The hydroxylation mechanisms of soluble and particulate methane
monooxygenase are considered in detail in Chapter “Enzymatic Methane Hydroxylation: sMMO and pMMO”. These mechanistic insights are reasonably extended
to the things in metal-exchanged zeolites in Chapters “Mechanistic Understanding
of Methane Hydroxylation by Cu-Exchanged Zeolites” and “Oxidative Activation
of Metal-Exchanged Zeolite Catalysts for Methane Hydroxylation” and IrO 2 and βPtO 2 (110) surfaces in Chapter “Dynamics and Energetics of Methane on the Surfaces
of Transition Metal Oxides”.
Acknowledgements K.Y. gives special thanks to JST-CREST “Innovative Catalysts” Grant No.
JPMJCR15P5 for its support of our theoretical project about natural-gas utilization. K.Y. acknowledges KAKENHI from Japan Society for the Promotion of Science (JSPS) and the Ministry
of Education, Culture, Sports, Science and Technology of Japan (MEXT) and also thanks the
MEXT Projects of “Integrated Research Consortium on Chemical Sciences,” “Cooperative Research
Program of Network Joint Research Center for Materials and Devices,” and “Elements Strategy
Initiative to Form Core Research Center”. The computations were performed at the Research
Institute for Information Technology (Kyushu University).
References
1. (a) Shilov AE (1984) Activation of saturated hydrocarbons by transitions metal complexes.
Reidel, Dordrecht (b) Shilov AE, Shul’pin GB (1997) Chem Rev 97:2879–2932
2. (a) Crabtree RH (1990) The organometallic chemistry of the transition metals. Wiley, New
York (b) Crabtree RH (1995) Chem Rev 95:987–1007
3. (a) Schröder D, Schwarz H (1995) Angew Chem Int Ed 34:1973–1995 (b) Schwarz H, Schröder
D (2000) Pure Appl Chem 72:2319–2332
4. Arndtsen BA, Bergman RG, Mobley TA, Peterson TH (1995) Acc Chem Res 28:154–162
5. Stahl SS, Labinger JA, Bercaw JE. (1998) Angew Chem Int Ed 37:2180–2192
6. (a) Feig AL, Lippard SJ (1994) Chem Rev 94:759–805 (b) Wallar BJ, Lipscomb JD (1996)
Chem Rev 96: 2625–2657 (c) Que L, Dong Y (1996) Acc Chem Res 29:190–196 (d) Merkx
M, Kopp DA, Sazinsky MH, Blazyk JL, Müller J, Lippard SJ (2001) Angew Chem Int Ed
40:2782–2807
7. (a) Lieberman RL, Shrestha DB, Doan PE, Hoffman BM, Stemmler TL, Rosenzeig AC (2003)
Proc Natl Acad Sci USA 100:3820–3825 (b) Chan SI, Chen KH-C, Yu SS-F, Chen C-Li, Kuo
SS-J (2004) Biochemistry 43:4421–4430
8. (a) Schröder D, Schwarz H (1990) Angew Chem Int Ed Engl 29:1433–1434 (b) Schröder D,
Fiedler A, Hrusák J, Schwarz H (1992) J Am Chem Soc 114:1215–1222
K. Yoshizawa and M. Miyanishi
FeO(CH 4 )
+ in the gas-phase reaction. Recently, a similar distortion of methane is
discussed in the adsorption and activation of CH 4 on IrO 2 (110) surface, which
exactly involves five-coordinate Ir atoms [49]. We looked at mechanistic aspects
about methane hydroxylation by the bare transition-metal oxide ions such as FeO
+
based on DFT calculations. Detailed discussion on the reactivity of the first-row
transition-metal oxide ions from ScO
+ to CuO
+ is given in Chapter “Theoretical
Study of the Direct Conversion of Methane by First-Row Transition-Metal Oxide
Cations in the Gas Phase”. An important feature in the reaction is the spin crossover
between the high-spin and low-spin potential energy surfaces in particular in the
C–H activation process, the energy barrier of which is significantly decreased by the
spin inversion. The hydroxylation mechanisms of soluble and particulate methane
monooxygenase are considered in detail in Chapter “Enzymatic Methane Hydroxylation: sMMO and pMMO”. These mechanistic insights are reasonably extended
to the things in metal-exchanged zeolites in Chapters “Mechanistic Understanding
of Methane Hydroxylation by Cu-Exchanged Zeolites” and “Oxidative Activation
of Metal-Exchanged Zeolite Catalysts for Methane Hydroxylation” and IrO 2 and βPtO 2 (110) surfaces in Chapter “Dynamics and Energetics of Methane on the Surfaces
of Transition Metal Oxides”.
Acknowledgements K.Y. gives special thanks to JST-CREST “Innovative Catalysts” Grant No.
JPMJCR15P5 for its support of our theoretical project about natural-gas utilization. K.Y. acknowledges KAKENHI from Japan Society for the Promotion of Science (JSPS) and the Ministry
of Education, Culture, Sports, Science and Technology of Japan (MEXT) and also thanks the
MEXT Projects of “Integrated Research Consortium on Chemical Sciences,” “Cooperative Research
Program of Network Joint Research Center for Materials and Devices,” and “Elements Strategy
Initiative to Form Core Research Center”. The computations were performed at the Research
Institute for Information Technology (Kyushu University).
References
1. (a) Shilov AE (1984) Activation of saturated hydrocarbons by transitions metal complexes.
Reidel, Dordrecht (b) Shilov AE, Shul’pin GB (1997) Chem Rev 97:2879–2932
2. (a) Crabtree RH (1990) The organometallic chemistry of the transition metals. Wiley, New
York (b) Crabtree RH (1995) Chem Rev 95:987–1007
3. (a) Schröder D, Schwarz H (1995) Angew Chem Int Ed 34:1973–1995 (b) Schwarz H, Schröder
D (2000) Pure Appl Chem 72:2319–2332
4. Arndtsen BA, Bergman RG, Mobley TA, Peterson TH (1995) Acc Chem Res 28:154–162
5. Stahl SS, Labinger JA, Bercaw JE. (1998) Angew Chem Int Ed 37:2180–2192
6. (a) Feig AL, Lippard SJ (1994) Chem Rev 94:759–805 (b) Wallar BJ, Lipscomb JD (1996)
Chem Rev 96: 2625–2657 (c) Que L, Dong Y (1996) Acc Chem Res 29:190–196 (d) Merkx
M, Kopp DA, Sazinsky MH, Blazyk JL, Müller J, Lippard SJ (2001) Angew Chem Int Ed
40:2782–2807
7. (a) Lieberman RL, Shrestha DB, Doan PE, Hoffman BM, Stemmler TL, Rosenzeig AC (2003)
Proc Natl Acad Sci USA 100:3820–3825 (b) Chan SI, Chen KH-C, Yu SS-F, Chen C-Li, Kuo
SS-J (2004) Biochemistry 43:4421–4430
8. (a) Schröder D, Schwarz H (1990) Angew Chem Int Ed Engl 29:1433–1434 (b) Schröder D,
Fiedler A, Hrusák J, Schwarz H (1992) J Am Chem Soc 114:1215–1222