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Mechanistic Insights into C–H Oxidations by Ruthenium(III)-Pterin Complexes: Impact of Basicity of the Pterin Ligand and Electron Acceptability of the Metal Center on the Transition States

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† Department of Chemistry, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan
‡ Institute for Materials Chemistry and Engineering, Kyushu University, Motooka, Nishi-Ku, Fukuoka 819-0395, Japan
*[email protected]
Cite this: J. Am. Chem. Soc. 2016, 138, 30, 9508–9520
Publication Date (Web):July 12, 2016
https://doi.org/10.1021/jacs.6b03785
Copyright © 2016 American Chemical Society
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Abstract

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A ruthenium(II) complex, [Ru(dmdmp)Cl(MeBPA)] (2) (Hdmdmp = N,N-dimethyl-6,7-dimethylpterin, MeBPA = N-methyl-N,N-bis(pyridylmethyl)amine), having a pterin derivative as a proton-accepting ligand, was synthesized and characterized. Complex 2 shows higher basicity than that of a previously reported RuII-pterin complex, [Ru(dmdmp) (TPA)]+ (1) (TPA = tris(2-pyridylmethyl)amine). On the other hand, 1e–-oxidized species of 1 (1OX) exhibits higher electron-acceptability than that of 1e–-oxidized 2 (2OX). Bond dissociation enthalpies (BDE) of the two RuII complexes having Hdmdmp as a ligand in proton-coupled electron transfer (PCET) to generate 1OX and 2OX were calculated to be 85 kcal mol–1 for 1OX and 78 kcal mol–1 for 2OX. The BDE values are large enough to perform H atom transfer from C–H bonds of organic molecules to the 1e–-oxidized complexes through PCET. The second-order rate constants (k) of PCET oxidation reactions were determined for 1OX and 2OX. The logarithms of normalized k values were proportional to the BDE values of C–H bonds of the substrates with slopes of −0.27 for 1OX and −0.44 for 2OX. The difference between 1OX and 2OX in the slopes suggests that the transition states in PCET oxidations of substrates by the two complexes bear different polarization, as reflection of difference in the electron acceptability and basicity of 1OX and 2OX. The more basic 2OX attracts a proton from a C–H bond via a more polarized transition state than that of 1OX; on the contrary, the more electron-deficient 1OX forms less polarized transition states in PCET oxidation reactions of C–H bonds.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b03785.

  • Procedure of pKa determination, DFT calculations, absorbance changes upon acid titration, crystal packing, electrochemical data, UV–vis spectral change upon oxidation of 2, UV–vis and ESR spectral changes in oxidation reactions, spin-trapping ESR spectra, linear dependence of pseudo-first-order rate constants for substrate oxidation on the concentration of the substrate, Eyring plots, and tables of atomic coordinates for DFT-optimized structures. (PDF)

  • Complete crystallographic data for the complexes 2 and 2-H+. (ZIP)

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This article is cited by 16 publications.

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  3. Chun-Bo Bo, Qingqing Bu, Xue Li, Ge Ma, Donghui Wei, Cheng Guo, Bin Dai, Ning Liu. Highly Active and Robust Ruthenium Complexes Based on Hemilability of Hybrid Ligands for C–H Oxidation. The Journal of Organic Chemistry 2020, 85 (6) , 4324-4334. https://doi.org/10.1021/acs.joc.0c00025
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  8. Manali Dutta, Kusum K. Bania, Sanjay Pratihar. A Remote ‘Imidazole’‐Based Ruthenium(II) Para‐Cymene Pre‐catalyst for the Selective Oxidation Reaction of Alkyl Arenes and Alcohols. Chemistry – An Asian Journal 2020, 15 (6) , 926-932. https://doi.org/10.1002/asia.201901760
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  10. Jie-Xiang Wang, Xian-Tai Zhou, Qi Han, Xiao-Xuan Guo, Xiao-Hui Liu, Can Xue, Hong-Bing Ji. Efficient and selective oxidation of alcohols to carbonyl compounds at room temperature by a ruthenium complex catalyst and hydrogen peroxide. New Journal of Chemistry 2019, 43 (48) , 19415-19421. https://doi.org/10.1039/C9NJ04393D
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  13. Manali Dutta, Kusum Kumar Bania, Sanjay Pratihar. Remote ‘Imidazole’ Based Ruthenium(II) p ‐Cymene Precatalyst for Selective Oxidative Cleavage of C−C Multiple Bonds. ChemCatChem 2019, 11 (11) , 2683-2694. https://doi.org/10.1002/cctc.201900242
  14. Yoshihiro Shimoyama, Tomoya Ishizuka, Hiroaki Kotani, Takahiko Kojima. Ruthenium(II) Complexes Having a Pincer-Type Ligand with Two N -Heterocyclic Carbene Moieties. Zeitschrift für anorganische und allgemeine Chemie 2018, 644 (14) , 611-615. https://doi.org/10.1002/zaac.201800104
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  16. Tomoya Ishizuka, Hiroaki Kotani, Takahiko Kojima. Characteristics and reactivity of ruthenium–oxo complexes. Dalton Transactions 2016, 45 (42) , 16727-16750. https://doi.org/10.1039/C6DT03024F

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