Schwach, P., Pan, X. & Bao, X. Direct conversion of methane to value-added chemicals over heterogeneous catalysts: challenges and prospects. Chem. Rev. 117, 8497–8520 (2017).
Ravi, M., Ranocchiari, M. & van Bokhoven, J. A. The direct catalytic oxidation of methane to methanol—a critical assessment. Angew. Chem. Int. Ed. 56, 16464–16483 (2017).
Riaz, A., Zahedi, G. & Klemeš, J. J. A review of cleaner production methods for the manufacture of methanol. J. Clean. Prod. 57, 19–37 (2013).
Wang, B., Albarracín-Suazo, S., Pagán-Torres, Y. & Nikolla, E. Advances in methane conversion processes. Catal. Today 285, 147–158 (2017).
Shilov, A. E. & Shul’pin, G. B. Activation of C–H bonds by metal complexes. Chem. Rev. 97, 2879–2932 (1997).
Periana, R. A. et al. Platinum catalysts for the high-yield oxidation of methane to a methanol derivative. Science 280, 560–564 (1998).
Mironov, O. A. et al. Using reduced catalysts for oxidation reactions: mechanistic studies of the “Periana-catalytica” system for CH4 Oxidation. J. Am. Chem. Soc. 135, 14644–14658 (2013).
Gunsalus, N. J. et al. Homogeneous functionalization of methane. Chem. Rev. 117, 8521–8573 (2017).
Horn, R. & Schlögl, R. Methane activation by heterogeneous catalysis. Catal. Lett. 145, 23–39 (2015).
Arakawa, H. et al. Catalysis research of relevance to carbon management: progress, challenges, and opportunities. Chem. Rev. 101, 953–996 (2001).
Rosenzweig, A. C., Frederick, C. A., Lippard, S. J. & Nordlund, P. Crystal structure of a bacterial non-haem iron hydroxylase that catalyses the biological oxidation of methane. Nature 366, 537–543 (1993).
Whittington, D. A., Rosenzweig, A. C., Frederick, C. A. & Lippard, S. J. Xenon and halogenated alkanes track putative substrate binding cavities in the soluble methane monooxygenase hydroxylase. Biochemistry 40, 3476–3482 (2001).
Banerjee, R. & Lipscomb, J. D. Small-molecule tunnels in metalloenzymes viewed as extensions of the active site. Acc. Chem. Res. 54, 2185–2195 (2021).
Zimmermann, T., Soorholtz, M., Bilke, M. & Schüth, F. Selective methane oxidation catalyzed by platinum salts in oleum at turnover frequencies of large-scale industrial processes. J. Am. Chem. Soc. 138, 12395–12400 (2016).
Díaz-Urrutia, C. & Ott, T. Activation of methane: a selective industrial route to methanesulfonic acid. Science 363, 1326–1329 (2019).
Luo, Y.-R. Handbook of Bond Dissociation Energies in Organic Compounds 1st edn (CRC, 2002).
Agarwal, N. et al. Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions. Science 358, 223–227 (2017).
Jin, Z. et al. Hydrophobic zeolite modification for in situ peroxide formation in methane oxidation to methanol. Science 367, 193–197 (2020).
Snyder, B. E. R. et al. The active site of low-temperature methane hydroxylation in iron-containing zeolite. Nature 536, 317–321 (2016).
Shan, J. et al. Mild oxidation of methane to methanol or acetic acid on supported isolated rhodium catalysts. Nature 551, 605–608 (2017).
Sushkevich, V. L., Palagin, D., Ranocchiari, M. & van Bokhoven, J. A. Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science 356, 523–527 (2017).
Chen, Y.-H., Wu, C.-Q., Sung, P.-H., Chan, S. I. & Chen, P. P.-Y. Turnover of a methane oxidation tricopper cluster catalyst: implications for the mechanism of the particulate methane monooxygenase (pMMO). ChemCatChem 12, 3088–3096 (2020).
Sorokin, A. B., Kudrik, E. V. & Bouchu, D. Bio-inspired oxidation of methane in watercatalysed by N-bridged diiron phthalocyanine complex. Chem. Commun. 2008, 2562–2564 (2008).
İşci, Ü. et al. Site-selective formation of an iron(IV)–oxo species at the more electron-rich iron atom of heteroleptic μ-nitride diiron phthalocyanines. Chem. Sci. 6, 5063–5075 (2015).
Afanasiev, P. & Sorokin, A. B. μ-Nitrido diiron macrocyclic platform: particular structure for particular catalysis. Acc. Chem. Res. 49, 583–593 (2016).
Friedle, S., Reisner, E. & Lippard, S. J. Current challenges of modelling diiron enzyme active sites for dioxygen activation by biomimetic synthetic complexes. Chem. Soc. Rev. 39, 2768–2779 (2010).
Fujisaki, H. et al. Selective catalytic 2e−-oxidation of organic substrates by an FeII complex having an N-heterocyclic carbene ligand in water. Chem. Commun. 56, 9783–9786 (2020).
Garal, L., Dutasta, J.-P. & Collet, A. Complexation of methane and chlorofluorocarbons by cryptophane-A in organic solution. Angew. Chem. Int. Ed. 32, 1169–1171 (1993).
Kano, K., Kitae, T., Shimofuri, Y., Tanaka, N. & Mineta, Y. Complexation of polyvalent cyclodextrin ions with oppositely charged guests: entropically favourable complexation due to dehydration. Chem. Eur. J. 6, 2705–2713 (2000).
Branda, N., Wyler, R. & Rebek, J. Jr Encapsulation of methane and other small molecules in a self-assembling superstructure. Science 263, 1267–1268 (1994).
Brazeau, B. J., Wallar, B. J. & Lipscomb, J. D. Unmasking of deuterium kinetic isotope effects on the methane monooxygenase compound Q reaction by site-directed mutagenesis of component B. J. Am. Chem. Soc. 123, 10421–10422 (2001).
Li, J.-L., Zhang, X. & Huang, X.-R. Mechanism of benzene hydroxylation by high-valent bare FeIV=O2+: explicit electronic structure analysis. Phys. Chem. Chem. Phys. 14, 246–256 (2012).
Shimoyama, Y. & Kojima, T. Metal–oxyl species and their possible roles in chemical oxidations. Inorg. Chem. 58, 9517–9542 (2019).
Nash, T. The colorimetric estimation of formaldehyde by means of the Hantzsch reaction. Biochem. J. 55, 416–421 (1953).
Ruan, Y., Peterson, P. W., Hadad, C. M. & Badjić, J. D. On the encapsulation of hydrocarbon components of natural gas within molecular baskets in water. The role of C–H···π interactions and the host’s conformational dynamics in the process of encapsulation. Chem. Commun. 50, 9086–9089 (2014).
Duan, Z. & Mao, S. A thermodynamic model for calculating methane solubility, density and gas phase composition of methane-bearing aqueous fluids from 273 to 523 K and from 1 to 2000 bar. Geochim. Cosmochim. Acta 70, 3369–3386 (2006).
Rohde, J.-U. et al. Crystallographic and spectroscopic characterization of a nonheme Fe(IV)–O complex. Science 299, 1037–1039 (2003).
Sastri, C. V. et al. Axial ligand substituted nonheme FeIV=O complexes: observation of near-UV LMCT bands and Fe=O Raman vibrations. J. Am. Chem. Soc. 127, 12494–12495 (2005).
Andris, E. et al. Trapping iron(III)–oxo species at the boundary of the “oxo wall”: insights into the nature of the Fe(III)–O bond. J. Am. Chem. Soc. 140, 14391–14400 (2018).
Evans, D. F. & Jakubovic, D. Water-soluble hexadentate Schiff-base ligands assequestrating agents for iron(III) and gallium(III). J. Chem. Soc. Dalton Trans. 1988, 2927–2933 (1988).
Frisch, M. J. et al. Gaussian 16 revision C.01 (Gaussian, 2009).
Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).
Lee, C., Yang, W. & Parr, R. G. Development of the Colle–Salvetti correlation–energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988).
Wachters, A. J. H. Gaussian basis set for molecular wavefunctions containing third-row atoms. J. Chem. Phys. 52, 1033–1036 (1970).
Hay, P. J. Gaussian basis sets for molecular calculations. The representation of 3d orbitals in transition-metal atoms. J. Chem. Phys. 66, 4377–4384 (1977).
Dunning, T. H. Jr & Hay, P. J. in Modern Theoretical Chemistry Vol. 3 (ed. Schaefer, H. F. III), (Plenum, 1977).
Cossi, M., Barone, V., Cammi, R. & Tomasi, J. Ab initio study of solvated molecules: a new implementation of the polarizable continuum model. Chem. Phys. Lett. 255, 327–335 (1996).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parameterization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).
Frost, A. A. & Pearson, R. G. Kinetics and Mechanism (Wiley, 1961).
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