文献类型：期刊文献

英文题名：Regulating microenvironment of heterogeneous Rh mononuclear complex via sulfur-phosphine co-coordination to enhance the performance of hydroformylation of olefins

作者：Feng, Siquan[1];Li, Cunyao[1];Zhou, Yuxuan[2];Song, Xiangen[1];Jiang, Miao[1];Dai, HuFei[1];Song, Shangsheng[1];Fan, Benhan[1];Cai, Yutong[1,3];Li, Bin[1];Yuan, Qiao[1,3];Li, Xingju[1];Zhu, Lei[1];Zhang, Yue[1];Chen, Weimiao[1];Liu, Tao[1];Yan, Li[1];Gong, Xueqing[4];Ding, Yunjie[1,5]

机构：[1]Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Liaoning, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]Univ Chinese Acad Sci, Beijing 100049, Peoples R China;[4]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, 800 Dongchuan Rd, Shanghai 200240, Peoples R China;[5]Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Catalysis, Dalian 116023, Liaoning, Peoples R China

年份：2025

卷号：78

起止页码：156

外文期刊名：CHINESE JOURNAL OF CATALYSIS

收录：;EI(收录号：20254619494190);WOS:【SCI-EXPANDED(收录号:WOS:001614991800010)】；

基金：This work was supported by the National Key R&D Program of China (2023YFA1506604, 2023YFA1507500), the National Natural Science Foundation of China (22002156, 22002152, 22108275, 22372161), the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2022179, 2023190, 2021181), the Liaoning Provincial Science and Technology Program Joint Program (Technology Tackling Program Project, No. 3E1731683594447), the CAS Project for Young Scientists in Basic Research (YSBR-022), the Natural Science Foundation of Liaoning Province-Outstanding Youth Science Foundation (2024JH3/10200014), the Dalian Outstanding Young Scientific and Technological Talents (2024RY016), and the Foundation of DICP I202117 and DICP I202455.

语种：英文

外文关键词：Heterogeneous hydroformylation; Rh mononuclear complex; Sulfur-Phosphine co-coordination; Synergistic effect; Sulfur poison; Sulfur promotion; Regulation of microenvironment

摘要：Sulfur was typically regarded as a poison to precious metal complex catalysts in hydroformylation of olefins. However, the combination of sulfur and phosphine may present an intriguing interaction with heterogeneous mononuclear complex due to the difference of their electronegativities, and coordination capabilities. Herein, we report a novel sulfur-phosphine co-coordinated heterogeneous Rh mononuclear complex catalyst (Rh1/POPs-PPh3&S), which exhibits an unexpected 1.5-2.0 times catalytic activity for hydroformylation of olefins (C3=, C5=-C8=), in comparison with the solely phosphine-coordinated Rh mononuclear complex catalyst (Rh1/POPs-PPh3). In contrast, sulfur coordination alone leads to severe sulfur poisoning with significantly inhibited catalytic performance. Experimental and theoretical analyses reveal that phosphine coordination promotes catalytic activity via its strong electron-donating ability, while sulfur occupies a coordination site and reduces the electronic density of Rh ions. The synergistical coordination of sulfur and phosphine optimizes the electronic density of active Rh ions and decreases the energy barrier of the rate-determining step of olefin insertion, thus enhancing the hydroformylation activity, regioselectivity and stability of Rh1/POPs-PPh3&S.