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Photochemical Activation of Ruthenium(II)–Pyridylamine Complexes Having a Pyridine-N-Oxide Pendant toward Oxygenation of Organic Substrates

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, Japan
‡Department of Material and Life Science, Graduate School of Engineering, Osaka University, and ⊥ALCA, Japan Science and Technology Agency (JST), 2-1 Yamada-oka, Suita, Osaka 565-0871, Japan
Graduate School of Life Science, University of Hyogo, Kouto, Hyogo 678-1297, Japan
Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, South Korea
[email protected]; [email protected]
Cite this: J. Am. Chem. Soc. 2011, 133, 44, 17901–17911
Publication Date (Web):September 26, 2011
https://doi.org/10.1021/ja207572z
Copyright © 2011 American Chemical Society
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Abstract

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Ruthenium(II)–acetonitrile complexes having η3-tris(2-pyridylmethyl)amine (TPA) with an uncoordinated pyridine ring and diimine such as 2,2′-bipyridine (bpy) and 2,2′-bipyrimidine (bpm), [RuII(η3-TPA)(diimine)(CH3CN)]2+, reacted with m-chloroperbenzoic acid to afford corresponding Ru(II)–acetonitrile complexes having an uncoordinated pyridine-N-oxide arm, [RuII(η3-TPA-O)(diimine)(CH3CN)]2+, with retention of the coordination environment. Photoirradiation of the acetonitrile complexes having diimine and the η3-TPA with the uncoordinated pyridine-N-oxide arm afforded a mixture of [RuII(TPA)(diimine)]2+, intermediate-spin (S = 1) Ru(IV)–oxo complex with uncoordinated pyridine arm, and intermediate-spin Ru(IV)–oxo complex with uncoordinated pyridine-N-oxide arm. A Ru(II) complex bearing an oxygen-bound pyridine-N-oxide as a ligand and bpm as a diimine ligand was also obtained, and its crystal structure was determined by X-ray crystallography. Femtosecond laser flash photolysis of the isolated O-coordinated Ru(II)–pyridine-N-oxide complex has been investigated to reveal the photodynamics. The Ru(IV)–oxo complex with an uncoordinated pyridine moiety was alternatively prepared by reaction of the corresponding acetonitrile complex with 2,6-dichloropyridine-N-oxide (Cl2py-O) to identify the Ru(IV)–oxo species. The formation of Ru(IV)–oxo complexes was concluded to proceed via intermolecular oxygen atom transfer from the uncoordinated pyridine-N-oxide to a Ru(II) center on the basis of the results of the reaction with Cl2py-O and the concentration dependence of the consumption of the starting Ru(II) complexes having the uncoordinated pyridine-N-oxide moiety. Oxygenation reactions of organic substrates by [RuII(η3-TPA-O)(diimine)(CH3CN)]2+ were examined under irradiation (at 420 ± 5 nm) and showed selective allylic oxygenation of cyclohexene to give cyclohexen-1-ol and cyclohexen-1-one and cumene oxygenation to afford cumyl alcohol and acetophenone.

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Figures S1–S8 and crystallographic data for 2a, 3a, and 4b in CIF format. This material is available free of charge via the Internet at http://pubs.acs.org.

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Cited By

This article is cited by 27 publications.

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  2. Alireza Karbakhsh Ravari, Guibo Zhu, Roman Ezhov, Yuliana Pineda-Galvan, Allison Page, Whitney Weinschenk, Lifen Yan, Yulia Pushkar. Unraveling the Mechanism of Catalytic Water Oxidation via de Novo Synthesis of Reactive Intermediate. Journal of the American Chemical Society 2020, 142 (2) , 884-893. https://doi.org/10.1021/jacs.9b10265
  3. Priyadarshi Ranjan, Sreejith Shankar, Ronit Popovitz-Biro, Sidney R. Cohen, Ifat Kaplan-Ashiri, Tali Dadosh, Linda J. W. Shimon, Bojana Višić, Reshef Tenne, Michal Lahav, Milko E. van der Boom. Decoration of Inorganic Nanostructures by Metallic Nanoparticles to Induce Fluorescence, Enhance Solubility, and Tune Band Gap. The Journal of Physical Chemistry C 2018, 122 (12) , 6748-6759. https://doi.org/10.1021/acs.jpcc.8b00510
  4. Muniyandi Sankaralingam, Yong-Min Lee, Wonwoo Nam, and Shunichi Fukuzumi . Selective Oxygenation of Cyclohexene by Dioxygen via an Iron(V)-Oxo Complex-Autocatalyzed Reaction. Inorganic Chemistry 2017, 56 (9) , 5096-5104. https://doi.org/10.1021/acs.inorgchem.7b00220
  5. Karan Arora, Jessica K. White, Rajgopal Sharma, Shivnath Mazumder, Philip D. Martin, H. Bernhard Schlegel, Claudia Turro, and Jeremy J. Kodanko . Effects of Methyl Substitution in Ruthenium Tris(2-pyridylmethyl)amine Photocaging Groups for Nitriles. Inorganic Chemistry 2016, 55 (14) , 6968-6979. https://doi.org/10.1021/acs.inorgchem.6b00650
  6. Fritz Weisser, Sebastian Plebst, Stephan Hohloch, Margarethe van der Meer, Sinja Manck, Felix Führer, Vanessa Radtke, Daniel Leichnitz, and Biprajit Sarkar . Tuning Ligand Effects and Probing the Inner-Workings of Bond Activation Steps: Generation of Ruthenium Complexes with Tailor-Made Properties. Inorganic Chemistry 2015, 54 (10) , 4621-4635. https://doi.org/10.1021/ic502807d
  7. Hideki Sugimoto, Kenji Ashikari, and Shinobu Itoh . C–H Bond Activation of the Methyl Group of the Supporting Ligand in an Osmium(III) Complex upon Reaction with H2O2: Formation of an Organometallic Osmium(IV) Complex. Inorganic Chemistry 2013, 52 (2) , 543-545. https://doi.org/10.1021/ic302169k
  8. Carlo Bravin, Elena Badetti, Giulia Licini, Cristiano Zonta. Tris(2-pyridylmethyl)amines as emerging scaffold in supramolecular chemistry. Coordination Chemistry Reviews 2021, 427 , 213558. https://doi.org/10.1016/j.ccr.2020.213558
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  12. James N. McPherson, Biswanath Das, Stephen B. Colbran. Tridentate pyridine–pyrrolide chelate ligands: An under-appreciated ligand set with an immensely promising coordination chemistry. Coordination Chemistry Reviews 2018, 375 , 285-332. https://doi.org/10.1016/j.ccr.2018.01.012
  13. Andranik Petrosyan, Richy Hauptmann, Jola Pospech. Heteroarene N -Oxides as Oxygen Source in Organic Reactions. European Journal of Organic Chemistry 2018, 2018 (38) , 5237-5252. https://doi.org/10.1002/ejoc.201800152
  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
  15. Naoyuki Toriumi, Shunsuke Yanagi, Atsuya Muranaka, Daisuke Hashizume, Masanobu Uchiyama. Effects of N-Oxidation on Heteroaromatic Macrocycles: Synthesis, Electronic Structures, Spectral Properties, and Reactivities of Tetraazaporphyrin meso - N -Oxides. Chemistry - A European Journal 2017, 23 (34) , 8309-8314. https://doi.org/10.1002/chem.201701300
  16. Suraj K. Gupta, Joyanta Choudhury. A Mixed N-Heterocyclic Carbene/2,2′-Bipyridine-Supported Robust Ruthenium(II) Oxidation Precatalyst for Benzylic C−H Oxidation. ChemCatChem 2017, 9 (11) , 1979-1984. https://doi.org/10.1002/cctc.201700177
  17. Karol Nowosinski, Stephan Warnke, Kevin Pagel, Dávid Komáromy, Wei Jiang, Christoph A. Schalley. Photooxygenation and gas-phase reactivity of multiply threaded pseudorotaxanes. Journal of Mass Spectrometry 2016, 51 (4) , 269-281. https://doi.org/10.1002/jms.3746
  18. Gui Chen, Lingjing Chen, Li Ma, Hoi-Ki Kwong, Tai-Chu Lau. Photocatalytic oxidation of alkenes and alcohols in water by a manganese( v ) nitrido complex. Chemical Communications 2016, 52 (59) , 9271-9274. https://doi.org/10.1039/C6CC04173F
  19. 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
  20. Christopher R. Turlington, Peter S. White, Maurice Brookhart, Joseph L. Templeton. Half-sandwich Rh(Cp*) and Ir(Cp*) complexes with oxygen atom transfer reagents as ligands. Journal of Organometallic Chemistry 2015, 792 , 81-87. https://doi.org/10.1016/j.jorganchem.2015.02.007
  21. Charles A. Enow, Charlene Marais, Barend C.B. Bezuidenhoudt. Non-peripherally alkyl substituted ruthenium phthalocyanines as catalysts in the epoxidation of alkenes. Journal of Porphyrins and Phthalocyanines 2015, 19 (04) , 582-594. https://doi.org/10.1142/S108842461450103X
  22. Jian-Bo Feng, Xiao-Feng Wu. Transition metal-catalyzed oxidative transformations of methylarenes. Applied Organometallic Chemistry 2015, 29 (2) , 63-86. https://doi.org/10.1002/aoc.3244
  23. Xiujuan Wu, Xiaonan Yang, Yong-Min Lee, Wonwoo Nam, Licheng Sun. A nonheme manganese( iv )–oxo species generated in photocatalytic reaction using water as an oxygen source. Chemical Communications 2015, 51 (19) , 4013-4016. https://doi.org/10.1039/C4CC10411K
  24. Francis D'Souza, Hiroshi Imahori. Preface — Special Issue in Honor of Professor Shunichi Fukuzumi. Journal of Porphyrins and Phthalocyanines 2015, 19 (01-03) , i-xvi. https://doi.org/10.1142/S1088424615020010
  25. Chun-Wai Tse, Toby Wai-Shan Chow, Zhen Guo, Hung Kay Lee, Jie-Sheng Huang, Chi-Ming Che. Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations. Angewandte Chemie 2014, 126 (3) , 817-822. https://doi.org/10.1002/ange.201305153
  26. Chun-Wai Tse, Toby Wai-Shan Chow, Zhen Guo, Hung Kay Lee, Jie-Sheng Huang, Chi-Ming Che. Nonheme Iron Mediated Oxidation of Light Alkanes with Oxone: Characterization of Reactive Oxoiron(IV) Ligand Cation Radical Intermediates by Spectroscopic Studies and DFT Calculations. Angewandte Chemie International Edition 2014, 53 (3) , 798-803. https://doi.org/10.1002/anie.201305153
  27. Simon A. Cotton. Iron, ruthenium and osmium. Annual Reports Section "A" (Inorganic Chemistry) 2012, 108 , 186. https://doi.org/10.1039/c2ic90010f

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