Theoretical perspective on mononuclear copper-oxygen mediated C-H and O-H activations: A comparison between biological and synthetic systems

doi:10.1016/S1872-2067(21)63974-8

Abstract

Abstract:

Dioxygen activations constitute one of core issues in copper-dependent metalloenzymes. Upon O₂ activation, copper-dependent metalloenzymes such as particulate methane monooxygenases (pMMOs), lytic polysaccharide monooxygenases (LPMOs) and binuclear copper enzymes PHM and DβM, are able to perform various challenging C-H bond activations. Meanwhile, various copper-oxygen core containing complexes have been synthetized to mimic the active species of metalloenzymes. Dioxygen activation by mononuclear copper active site may generate various copper-oxygen intermediates, including Cu(II)-superoxo, Cu(II)-hydroperoxo, Cu(II)-oxyl as well as the Cu(III)-hydroxide species. Intriguingly, all these species have been invoked as the potential active intermediates for C-H/O-H activations in either biological or synthetic systems. Due to the poor understanding on reactivities of copper-oxygen complex, the nature of active species in both biological and synthetic systems are highly controversial. In this account, we will compare the reactivities of various mononuclear copper-oxygen species between biological systems and the synthetic systems. The present study is expected to provide the consistent understanding on reactivities of various copper-oxygen active species in both biological and synthetic systems.

Key words: Dioxygen activation, Cu(II)-superoxo, Cu(II)-hydroperoxo, Cu(II)-oxyl, Cu(III)-hydroxide, C-H activation, Lytic polysaccharide monooxygenase, Particulate methane monooxygenase

Peng Wu, Jinyan Zhang, Qianqian Chen, Wei Peng, Binju Wang. Theoretical perspective on mononuclear copper-oxygen mediated C-H and O-H activations: A comparison between biological and synthetic systems[J]. Chinese Journal of Catalysis, 2022, 43(4): 913-927.

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Figures/Tables 15

Fig. 1. The active site structures of pMMO-CuC site (a), LPMO (b) and PHM and DβM (c). The reactions catalyzed by these copper-dependent enzymes are shown below the corresponding active site structures.

Scheme 1. Formation of various copper-oxygen complexes during Cu(I)-mediated O2 activations.

Fig. 2. QM/MM calculated energy barriers (ΔE≠) in kcal/mol for Cu(II)-O2•mediated HAA from the C-H bond of hippuric acid (a) and the O-H bond of the ascorbate in the CuM site of PHM (b). Reprinted with permission from Ref. [222]. Copyright 2019, American Chemical Society.

Fig. 3. (a) [(TMPA)-Cu(II)-O2•]+mediated HAA from O-H bond of DTBP; (b) MN15/def2-SVP optimized transition state (TS) structure and MN15/def2-TZVP//def2-SVP calculated Gibbs energy barrier (in kcal/mol) at -135 °C in the triplet ground state. The experimental solvent of THF was used in calculations. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted. ΔG≠exp: the experimental Gibbs energy barrier derived from the reaction rate constant in Ref. [165]; ΔG≠cal: the calculated Gibbs energy barrier; ΔΔE≠tun: the barrier reduction from the tunneling effect; ΔG≠final: the calculated final Gibbs energy barrier upon inclusion of the tunneling effect.

Fig. 4. (a) (TMPA)-Cu(II)-O2•mediated HAA from the O-H bond of 4-methoxyphenol (MP); (b) MN15/def2-SVP optimized TS structure and MN15/def2-TZVP//def2-SVP calculated Gibbs energy barrier in kcal/mol at -135 °C in the triplet ground state. The experimental solvent of THF was used in calculations. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted; ΔG≠cal: the calculated Gibbs energy barrier; ΔΔE≠tun: the barrier reduction from the tunneling effect; ΔG≠final: the calculated final Gibbs energy barrier upon inclusion of the tunneling effect.

Fig. 5. (a) (N-tridentate)-Cu(II)-O2•mediated HAA from benzylic C-H bond the ligand; (b) MN15/def2-SVP optimized TS structure and MN15/def2-TZVP//def2-SVP calculated Gibbs energy barrier in kcal/mol at -65 °C in the triplet ground state. The experimental solvent of acetone was used in calculations. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted. ΔG≠exp: the experimental Gibbs energy barrier derived from the reaction rate constant in Ref. [237]; ΔG≠cal: the calculated Gibbs energy barrier; ΔΔE≠tun: the barrier reduction from the tunneling effect; ΔG≠final: the calculated final Gibbs energy barrier upon inclusion of the tunneling effect.

Fig. 6. (a) PHM/DβM-Cu(II)-O2•mediated HAA from the benzylic C-H bond of ethylbenzene. Note the bond strength of benzylic C-H bond of ethylbenzene (BDE: 81.6 kcal/mol) is even weaker than that of hippuric acid (BDE: 89.8 kcal/mol), one of mostly used substrate for PHM/DβM; (b) MN15/def2-SVP optimized TS structure and MN15/def2-TZVP// def2-SVP calculated Gibbs energy barrier in kcal/mol at -135 °C in the triplet ground state. The solvent of chloroform was used in calculations. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted. ΔG≠cal: the calculated Gibbs energy barrier; ΔΔE≠tun: the barrier reduction from the tunneling effect; ΔG≠final: the calculated final Gibbs energy barrier upon inclusion of the tunneling effect.

Fig. 7. MN15/def2-TZVP//def2-SVP calculated Gibbs reaction energy (in kcal/mol) for the formation of Cu(II)-O2•species as well as the Gibbs energy barrier for Cu(II)-O2•species mediated HAA from alcohol oxidation in Ref [182]. ΔG: Gibbs reaction energy; ΔG≠:Gibbs energy barrier. The experimental solvent of DMF was used in calculations.

Fig. 8. (a) QM/MM calculated energy barriers (in kcal/mol) for Cu(II)-OOH-mediated H-abstraction from substrate hippuric acid of at the CuM site of PHM. Reprinted with permission from Ref. [222]. Copyright 2019, American Chemical Society. (b) Reaction of CuM(II)-OOH with CuH(I) to afford the dicopper (μ-O•)(μ-OH)Cu(II)Cu(II) in PHM/DβM. Reprinted with permission from Ref. [222]. Copyright 2019, American Chemical Society. (c) HAA from ascorbate by the proximal O of Cu(II)-OOH to form Cu(I) and H2O2. Reprinted from Ref. [45]. Copyright 2016, American Chemical Society. (d) His147-mediated proton transfer to the proximal O of Cu(II)-OOH to form Cu(II) and H2O2. Reprinted from Ref. [45]. Copyright 2016, American Chemical Society.

Fig. 9. Mechanistic study for Cu(II)-OOH mediated N-dealkylation [157]. (a) DFT calculated barrier and reaction energy (in kcal/mol) for Cu(II)-OOH mediated HAA from the substrate C-H bond via the distal oxygen; (b) DFT calculated barrier and reaction energy (in kcal/mol) for O-O homolysis of Cu(II)-OOH; (c) DFT calculated barrier and reaction energy (in kcal/mol) for Cu(II)-OOH mediated HAA from the substrate C-H bond via the proximal oxygen; (d) Suggested Fenton-type mechanism for the formation of •OH radical that is responsible for the C-H bond activation of substrate. Reprinted with permission from Ref. [157]. Copyright 2015, American Chemical Society.

Fig. 10. (a) Cu(II)-OOH mediated the first step of hydroxylation of sp2C-H bonds; (b) MN15/def2-SVP optimized TS structure and MN15/ def2-TZVP//def2-SVP calculated Gibbs energy barrier in kcal/mol in the singlet ground state. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted; ΔG≠exp: the experimental Gibbs energy barrier derived from the reaction rate constant in Ref. [191]; ΔG≠calc: the calculated Gibbs energy barrier; The experimental solvent of acetone was used in calculations.

Fig. 11. Calculated Gibbs energy barrier and Gibbs reaction energy (in kcal/mol) for Cu(II)-O•mediated HAA from CH4 in pMMO. Reprinted with permission from Ref. [227]. Copyright 2021, Springer Nature.

Fig. 12. Reactivities of various Cu(II)-O•species for substrate oxidations. (a) DFT calculated barrier and reaction energy (in kcal/mol) for CH4 activation by the gas-phase diatomic [CuO]+; (b) DFT calculated barrier and reaction energy (in kcal/mol) for CH4 activation by [(phen)CuO]+; (c) DFT calculated barrier and reaction energy (in kcal/mol) for cyclohexane activation by the [CuO]+species. Reprinted with permission from Ref. [273]. Copyright 2009, American Chemical Society; (d) DFT calculated barrier and reaction energy (in kcal/mol) for benzene oxidation by the [CuO]+species. Reprinted with permission from Ref. [132]. Copyright 2009, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 13. (a) MN15/def2-TZVP//def2-SVP calculated relative energies (kcal/mol) for the protonation of Cu(III)-OH by Acetic acid; (b) DFT calculated relative energies (kcal/mol) for the reduction of Cu(III)-OH by ascorbic acid. The solvent of chlorobenzene was used in calculations.

Fig. 14. (a) LPMO-Copper(III)-hydroxide mediated HAA from C-H bond of the cyclohexane; (b) MN15/def2-SVP optimized TS structure and MN15/def2-TZVP//def2-SVP calculated Gibbs energy barrier in kcal/mol in the singlet ground state. Key distances (in Å), the imaginary frequency of TS and key spin density population are provided. For clarity, unimportant hydrogen atoms are omitted; ΔG≠exp: the experimental Gibbs energy barrier from Ref [282]; ΔG≠calc: the calculated Gibbs energy barrier; ΔΔE≠tun: the barrier reduction from the tunneling effect; ΔG≠final: the calculated final Gibbs energy barrier upon inclusion of the tunneling effect. The solvent of 1,2-difluorobenzene (1, 2-DFB) was used in calculations.

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