Elucidation of hemilabile-coordination-induced tunable regioselectivity in single-site Rh-catalyzed heterogeneous hydroformylation

Benhan Fan, Miao Jiang, Guoqing Wang, Yang Zhao, Bingbao Mei, Jingfeng Han, Lei Ma, Cunyao Li, Guangjin Hou, Tao Wu (), Li Yan () and Yunjie Ding ()
Additional contact information
Benhan Fan: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Miao Jiang: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Guoqing Wang: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Yang Zhao: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Bingbao Mei: Shanghai Advanced Research Institute, Chinese Academy of Sciences
Jingfeng Han: iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Lei Ma: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Cunyao Li: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Guangjin Hou: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Tao Wu: Dalian University of Technology
Li Yan: Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Yunjie Ding: Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Nature Communications, 2024, vol. 15, issue 1, 1-14

Abstract: Abstract Revealing key factors that modulate the regioselectivity in heterogeneous hydroformylation requires identifying and monitoring the dynamic evolution of the truly active center under real reaction conditions. However, unambiguous in situ characterizations are still lacking. Herein, we elaborately construct a series of Rh-POPs catalysts for propylene hydroformylation which exhibited tunable regioselectivity. Multi-technique approaches reveal the unique microenvironment of the diverse HRh(CO)(PPh3-frame)2 sites with distinct P-Rh-P bite angles ranging from 90° to 120° and 158° to 168°, respectively. In situ time-resolved XAFS, FT-IR, and quasi-in situ Solid-state NMR experiments combined with DFT calculations explain the dynamic evolution of the electronic and coordinate state of the distinct active sites induced by hemilabile PPh3-frame ligands and further disclose the regulatory mechanism of regioselectivity. These state-of-the-art techniques and multiscale analysis advance the understanding of how hemilabile coordination influences regioselectivity and will provide a new thought to modulate the regioselectivity in future industrial processes.

Date: 2024
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-024-51281-1 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-51281-1

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-024-51281-1

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().