Catalytic Oxidative Cracking of Benzene Rings in Water
- Yoshihiro ShimoyamaYoshihiro ShimoyamaDepartment of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Yoshihiro Shimoyama,
- Tomoya IshizukaTomoya IshizukaDepartment of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Tomoya Ishizuka,
- Hiroaki KotaniHiroaki KotaniDepartment of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Hiroaki Kotani, and
- Takahiko Kojima*Takahiko Kojima*E-mail: [email protected]Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennoudai, Tsukuba, Ibaraki 305-8571, JapanMore by Takahiko Kojima
Abstract
Efficient degradation of harmful benzene rings in water is indispensable for achieving a clean water environment. We report herein unprecedented catalytic oxidative benzene cracking (OBC) in water using a ruthenium(II)–aqua complex having an N-heterocyclic carbene ligand as a catalyst and a cerium(IV) salt as a sacrificial oxidant under mild conditions. The OBC reactions produced carboxylic acids such as formic acid, which can be converted to dihydrogen directly from the OBC solution using a rhodium(III) catalyst with adjustment of the solution pH to 3.3. The OBC reactions can be applied to monosubstituted benzene derivatives such as ethylbenzene, chlorobenzene, and benzoic acid. Initial rates of the OBC reactions showed a linear relationship in the Hammett plot with a negative slope, indicating the electrophilicity of a Ru(III)–oxyl complex as the reactive species in the catalytic OBC reaction. Also, we discuss a plausible mechanism of the catalytic OBC reactions based on the kinetic analysis and the product stoichiometry for the OBC reaction of nonvolatile sodium m-xylene sulfonate. The addition of an electrophilic radical to the aromatic ring to form arene oxide/oxepin is proposed as the initial step of the OBC reaction.
Cited By
This article is cited by 7 publications.
- Nengchao Luo, Tingting Hou, Shiyang Liu, Bin Zeng, Jianmin Lu, Jian Zhang, Hongji Li, Feng Wang. Photocatalytic Coproduction of Deoxybenzoin and H2 through Tandem Redox Reactions. ACS Catalysis 2020, 10 (1) , 762-769. https://doi.org/10.1021/acscatal.9b03651
- Yoshihiro Shimoyama, Takahiko Kojima. Metal–Oxyl Species and Their Possible Roles in Chemical Oxidations. Inorganic Chemistry 2019, 58 (15) , 9517-9542. https://doi.org/10.1021/acs.inorgchem.8b03459
- Yoshihiro Shimoyama, Satoru Tamura, Yasutaka Kitagawa, Dachao Hong, Yoshihiro Kon. A cobalt-substituted Keggin-type polyoxometalate for catalysis of oxidative aromatic cracking reactions in water. Catalysis Science & Technology 2020, 10 (23) , 8042-8048. https://doi.org/10.1039/D0CY01758B
- Hiroto Fujisaki, Tomoya Ishizuka, Yoshihiro Shimoyama, Hiroaki Kotani, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima. Selective catalytic 2e − -oxidation of organic substrates by an Fe II complex having an N-heterocyclic carbene ligand in water. Chemical Communications 2020, 56 (68) , 9783-9786. https://doi.org/10.1039/D0CC03289A
- Takahiko Kojima. Development of functionality of metal complexes based on proton-coupled electron transfer. Dalton Transactions 2020, 49 (22) , 7284-7293. https://doi.org/10.1039/D0DT00898B
- Namita Sharma, Yong‐Min Lee, Wonwoo Nam, Shunichi Fukuzumi. Photoinduced Generation of Superoxidants for the Oxidation of Substrates with High C−H Bond Dissociation Energies. ChemPhotoChem 2020, 4 (4) , 271-281. https://doi.org/10.1002/cptc.201900219
- Shunichi Fukuzumi, Yong‐Min Lee, Wonwoo Nam. Photocatalytic Oxygenation Reactions Using Water and Dioxygen. ChemSusChem 2019, 12 (17) , 3931-3940. https://doi.org/10.1002/cssc.201901276