TY - JOUR
T1 - Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy
AU - Zhang, Yufan
AU - Chen, Xin
AU - Zheng, Bin
AU - Guo, Xunmin
AU - Pan, Yupeng
AU - Chen, Hailong
AU - Li, Huaifeng
AU - Min, Shixiong
AU - Guan, Chao
AU - Huang, Kuo-Wei
AU - Zheng, Junrong
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Y.Z. acknowledges a Schlumberger future faculty award. This work is supported by National Natural Science Foundation of China (NSFC) (NSFC-21627805, 21673004, and 21821004), NSF (CHE-1503865), and Ministry of Science and Technology of the People’s Republic of China (2017YFA0204702) (to J.Z.), and by King Abdullah University of Science and Technology (to K.-W.H.).
PY - 2018/11/19
Y1 - 2018/11/19
N2 - The molecular structure of a catalytically active key intermediate is determined in solution by employing 2D IR spectroscopy measuring vibrational cross-angles. The formate intermediate (2) in the formic acid dehydrogenation reaction catalyzed by a phosphorus-nitrogen PN3P-Ru catalyst is elucidated. Our spectroscopic studies show that the complex features a formate ion directly attached to the Ru center as a ligand, and a proton added to the imine arm of the dearomatized PN3P* ligand. During the catalytic process, the imine arms are not only reversibly protonated and deprotonated, but also interacting with the protic substrate molecules, effectively serving as the local proton buffer to offer remarkable stability with a turnover number (TON) over one million.
AB - The molecular structure of a catalytically active key intermediate is determined in solution by employing 2D IR spectroscopy measuring vibrational cross-angles. The formate intermediate (2) in the formic acid dehydrogenation reaction catalyzed by a phosphorus-nitrogen PN3P-Ru catalyst is elucidated. Our spectroscopic studies show that the complex features a formate ion directly attached to the Ru center as a ligand, and a proton added to the imine arm of the dearomatized PN3P* ligand. During the catalytic process, the imine arms are not only reversibly protonated and deprotonated, but also interacting with the protic substrate molecules, effectively serving as the local proton buffer to offer remarkable stability with a turnover number (TON) over one million.
UR - http://hdl.handle.net/10754/630013
UR - http://www.pnas.org/content/early/2018/11/16/1809342115
UR - http://www.scopus.com/inward/record.url?scp=85057585485&partnerID=8YFLogxK
U2 - 10.1073/pnas.1809342115
DO - 10.1073/pnas.1809342115
M3 - Article
C2 - 30455307
SN - 0027-8424
VL - 115
SP - 12395
EP - 12400
JO - Proceedings of the National Academy of Sciences
JF - Proceedings of the National Academy of Sciences
IS - 49
ER -