Synergistic Effect of FeII and MnII Ions in Cyano-Bridged Heterometallic Coordination Polymers on Catalytic Selectivity of Benzene Oxygenation to Phenol

Hiroyasu Tabe; Yusuke Seki; Mari Yamane; Takashi Nakazono; Yusuke Yamada

doi:10.1021/acs.jpclett.2c02939

Synergistic Effect of Fe^II and Mn^II Ions in Cyano-Bridged Heterometallic Coordination Polymers on Catalytic Selectivity of Benzene Oxygenation to Phenol

J Phys Chem Lett. 2023 Jan 12;14(1):158-163. doi: 10.1021/acs.jpclett.2c02939. Epub 2022 Dec 29.

Authors

Hiroyasu Tabe¹, Yusuke Seki², Mari Yamane², Takashi Nakazono³, Yusuke Yamada^{2

3}

Affiliations

¹ Institute for Integrated Cell-Material Sciences (iCeMS), Institute for Advanced Study (IAS), Kyoto University, Yoshida-Hommachi, Sakyo-ku, Kyoto 606-8501, Japan.
² Department of Chemistry and Bioengineering, Graduate School of Engineering, Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan.
³ Research Center for Artificial Photosynthesis (ReCAP), Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan.

PMID: 36579843
DOI: 10.1021/acs.jpclett.2c02939

Abstract

A cyano-bridged heterometallic coordination polymer with partial deficiencies of CN^- ligands, [Mn^II(H₂O)_8/3]_3/2[Fe^II(CN)₅(NH₃)], forms open metal sites both on Mn^II and Fe^II ions by liberation of monodentate ligands such as NH₃ and H₂O. [Mn^II(H₂O)_8/3]_3/2[Fe^II(CN)₅(NH₃)] exhibits high catalytic activity and selectivity of benzene oxygenation to phenol in the presence of m-chloroperoxybenzoic acid as an oxidant. The postcatalytic spectroscopy of [Mn^II(H₂O)_8/3]_3/2[Fe^II(CN)₅(NH₃)] and catalysis comparison with a physical mixture of [Mn^II(H₂O)₃]₂[Fe^II(CN)₆] and [Fe(H₂O)_3/2]_4/3[Fe(CN)₆], which has open metal sites on both Mn^II and Fe ions separately, indicated that the high activity resulted from high oxidation ability and phenol adsorption ability of Fe^II and Mn^II ions, respectively.