文献类型：期刊文献

英文题名：Ruthenium Single-Atom Anchored in Polyoxometalate-Ionic Liquids for N-Formylation of Amines with CO2 and H2

作者：Ma, Yuan[1];Chen, Chen[2,3];Jiang, Yongjun[4,5];Wei, Xinjia[1];Liu, Ying[2,3];Liao, Huiying[1];Wang, Haifeng[2,3];Dai, Sheng[4,5];An, Pengfei[6];Hou, Zhenshan[1]

机构：[1]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Ctr Computat Chem, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[5]East China Univ Sci & Technol, Inst Fine Chem, Feringa Nobel Prize Scientist Joint Res Ctr, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[6]Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil BSRF, Beijing 100049, Peoples R China

年份：2023

卷号：13

期号：15

起止页码：10295

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20233314571795);WOS:【SCI-EXPANDED(收录号:WOS:001032535900001)】；

基金：The authors acknowledge the support from the National Natural Science Foundation of China (21773061 and 21978095) and the National Key Research and Development Program of China (2022YFA1504903).

语种：英文

外文关键词：polyoxometalate; ionic liquid; single metalatom; N-formylation; CO2

摘要：In this work, we have developed aRu single-atom substituted polyoxometalate-basedionic liquid ([TOMA(6)SiW(11)O(39)Ru(dmso)],TOMA = methyltrioctylammonium, named as Ru-POM-IL) and confirmed thatthe single-atom Ru is anchored into the framework of the POM. Thebinary ionic liquid (IL) system, composed of the POM-based IL and1-butyl-3-methyl-imidazolium acetate (BMImOAc), exhibits high efficiencyfor N-formylation of amines with CO2 and H-2,leading to formylamides with high yields in toluene-IL biphasic media.The characterization by laser confocal scanning microscopy revealsa specific sponge-like structure of the binary IL, facilitating theefficient contact between the catalytic active sites and the substratemolecules. Detailed investigations elucidate that the reaction proceedsvia a pathway with formate intermediates, including CO2 adsorption and activation by BMImOAc, morpholine-assisted heterolyticsplitting of H-2 into Ru-H & delta;- species and the H & delta;+ attachment to the morpholineN center; the coupling of CO2 with Ru-H & delta;- to afford formate species; and then the dehydration of the formateintermediates to formamides. The catalytic system exhibits offeredadvantages of high efficiency, robustness, and recyclability in theN-formylation reaction.