氰桥联异金属配位聚合物中 Fe 和 Mn 离子对苯氧化为苯酚催化选择性的协同效应。

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

机构信息

Institute for Integrated Cell-Material Sciences (iCeMS), Institute for Advanced Study (IAS), Kyoto University, Yoshida-Hommachi, Sakyo-ku, Kyoto 606-8501, Japan.

Department of Chemistry and Bioengineering, Graduate School of Engineering, Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi, Osaka 558-8585, Japan.

出版信息

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

DOI:10.1021/acs.jpclett.2c02939

PMID:36579843

Abstract

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

摘要

一个具有部分氰配体缺失的氰桥异金属配位聚合物[Mn(HO)][Fe(CN)(NH)]，通过释放单齿配体如 NH 和 HO，在 Mn 和 Fe 离子上形成开放的金属位点。[Mn(HO)][Fe(CN)(NH)]在 -氯过氧苯甲酸作为氧化剂存在下，对苯的氧化表现出高的催化活性和选择性，生成苯酚。[Mn(HO)][Fe(CN)(NH)]的后催化光谱和与[Mn(HO)][Fe(CN)]和[Fe(HO)][Fe(CN)]的物理混合物的催化比较，后者在 Mn 和 Fe 离子上分别具有开放的金属位点，表明高活性分别来自于 Fe 和 Mn 离子的高氧化能力和苯酚吸附能力。