锆/铪氧簇中硫原子导向的金属-配体协同高效催化胺氧化反应  

Sulfur atom-directed metal-ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation

作　　者：孙胜男 牛倩 林焦敏 何莉玲 石景文 黄青 刘江 兰亚乾 Sheng-Nan Sun;Qian Niu;Jiao-Min Lin;Li-Ling He;Jing-Wen Shi;Qing Huang;Jiang Liu;Ya-Qian Lan(School of Chemistry,South China Normal University,Guangzhou 510006,China;College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China;School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China)

机构地区：[1]School of Chemistry,South China Normal University,Guangzhou 510006,China [2]College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China [3]School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China

出　　处：《Science Bulletin》2024年第4期492-501,共10页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(22225109,92061101,22071109,and 22101089);the Top Youth Project of Guangdong Province Pearl River Talents Program(2021QN02L617);the Excellent Youth Foundation of Jiangsu Provincial Natural Science Foundation(BK20211593);the Open Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials Technology(SCNU-TINCI-202204);Guangdong Provincial Basic and Applied Basic Research Foundation(2023A1515030097 and 2020A1515110836).

摘　　要：The performance applications(e.g.,photocatalysis)of zirconium(Zr)and hafnium(Hf)based complexes are greatly hindered by the limited development of their structures and the relatively inert metal reactivity.In this work,we constructed two ultrastable Zr/Hf-based clusters(Zr_(9)-TC4A and Hf_(9)-TC4A)using hydrophobic 4-tert-butylthiacalix[4]arene(H4TC4A)ligands,in which unsaturated coordinated sulfur(S)atoms on the TC4A^(4-)ligand can generate strong metal–ligand synergy with nearby active metal Zr/Hf sites.As a result,these two functionalized H4TC4A ligands modified Zr/Hf-oxo clusters,as catalysts for the amine oxidation reaction,exhibited excellent catalytic activity,achieving very high substrate conversion(>99%)and product selectivity(>90%).Combining comparative experiments and theoretical calculations,we found that these Zr/Hf-based cluster catalysts accomplish efficient amine oxidation reactions through synergistic effect between metals and ligands:(i)The photocatalytic benzylamine(BA)oxidation reaction was achieved by the synergistic effect of the dual active sites,in which,the naked S sites on the TC4A^(4-)ligand oxidize the BA by photogenerated hole and oxygen molecules are reduced by photogenerated electrons on the metal active sites;(ii)in the aniline oxidation reaction,aniline was adsorbed by the bare S sites on ligands to be closer to metal active sites and then oxidized by the oxygen-containing radicals activated by the metal sites,thus completing the catalytic reaction under the synergistic catalytic effect of the proximity metal–ligand.In this work,the Zr/Hf-based complexes applied in the oxidation of organic amines have been realized using active S atom-directed metal–ligand synergistic catalysis and have demonstrated very high reactivity.

关 键 词：Zirconium/hafnium-oxo clusters Amine oxidation reaction Photocatalytic reaction Synergistic catalysis 

分 类 号：O621.251[理学—有机化学]