4.8 Article

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

期刊

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 -, 期 -, 页码 158-163

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c02939

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资金

  1. JSPS KAKENHI [JP22H01871, JP21K14648, JP19KK0144]
  2. Innovative Science and Technology Initiative for Security (ATLA, Japan) [JPJ004596]
  3. New Energy and Industrial Technology Development Organization (NEDO) [JPNP14004]
  4. Research of the Japan Petroleum Institute
  5. ENEOS Tonen General Sekiyu Research/Development Encouragement and Scholarship Foundation

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This article presents the catalytic activity and selectivity of a cyanide-bridged heterometallic coordination polymer with open metal sites. Experimental results demonstrate that FeII ions have high oxidation ability and MnII ions have strong adsorption ability towards phenol.
A cyano-bridged heterometallic coordination polymer with partial deficiencies of CN- ligands, [MnII(H2O)8/3]3/2[FeII(CN)5(NH3)], forms open metal sites both on MnII and FeII ions by liberation of monodentate ligands such as NH3 and H2O. [MnII(H2O)8/3]3/2[FeII(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 [MnII(H2O)8/3]3/2[FeII(CN)5(NH3)] and catalysis comparison with a physical mixture of [MnII(H2O)3]2[FeII(CN)6] and [Fe(H2O)3/2]4/3- [Fe(CN)6], which has open metal sites on both MnII and Fe ions separately, indicated that the high activity resulted from high oxidation ability and phenol adsorption ability of FeII and MnII ions, respectively.

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