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Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy

Yufan Zhang, Xin Chen, Bin Zheng, Xunmin Guo, Yupeng Pan, Hailong Chen, Huaifeng Li, Shixiong Min, Chao Guan, Kuo-Wei Huang, and Junrong Zheng
PNAS December 4, 2018 115 (49) 12395-12400; published ahead of print November 19, 2018 https://doi.org/10.1073/pnas.1809342115
Yufan Zhang
aCollege of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, 100871 Beijing, China;bDepartment of Chemistry, Rice University, Houston, TX 77005;
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Xin Chen
aCollege of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, 100871 Beijing, China;
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Bin Zheng
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;
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Xunmin Guo
aCollege of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, 100871 Beijing, China;bDepartment of Chemistry, Rice University, Houston, TX 77005;
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Yupeng Pan
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;dDivision of Physical Science and Engineering, King Abdullah University of Science and Technology , 23955-6900 Thuwal, Saudi Arabia
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Hailong Chen
aCollege of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, 100871 Beijing, China;bDepartment of Chemistry, Rice University, Houston, TX 77005;
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Huaifeng Li
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;dDivision of Physical Science and Engineering, King Abdullah University of Science and Technology , 23955-6900 Thuwal, Saudi Arabia
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Shixiong Min
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;dDivision of Physical Science and Engineering, King Abdullah University of Science and Technology , 23955-6900 Thuwal, Saudi Arabia
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  • ORCID record for Shixiong Min
Chao Guan
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;dDivision of Physical Science and Engineering, King Abdullah University of Science and Technology , 23955-6900 Thuwal, Saudi Arabia
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Kuo-Wei Huang
cKing Abdullah University of Science and Technology Catalysis Center, King Abdullah University of Science and Technology, 23955-6900 Thuwal, Saudi Arabia;dDivision of Physical Science and Engineering, King Abdullah University of Science and Technology , 23955-6900 Thuwal, Saudi Arabia
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  • For correspondence: hkw@kaust.edu.sajunrong@pku.edu.cn
Junrong Zheng
aCollege of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, 100871 Beijing, China;
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  • For correspondence: hkw@kaust.edu.sajunrong@pku.edu.cn
  1. Edited by Michael D. Fayer, Stanford University, Stanford, CA, and approved October 29, 2018 (received for review May 31, 2018)

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Significance

We demonstrate that the transient intermediate structure, which is too fast for traditional techniques, e.g. NMR or X-ray diffraction, to resolve in a thermally driven reaction can be determined in situ with the vibrational cross-angle method. The principle of the method illustrated in the work is general for other organic reactions and the method is expected to bring profound impacts for the studies of chemical reactions. The reaction mechanism of a well-defined catalytic system with performance to generate H2 from formic acid is elucidated.

Abstract

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.

  • formic acid dehydrogenation
  • vibrational cross-angle method
  • intermediate molecular structure

Footnotes

  • ↵1Y.Z. and X.C. contributed equally to this work.

  • ↵2Present address: Beijing National Laboratory for Condensed Matter Physics, CAS Key Laboratory of Soft Matter Physics, Institute of Physics, Chinese Academy of Sciences, 100190 Beijing, China.

  • ↵3To whom correspondence may be addressed. Email: hkw{at}kaust.edu.sa or junrong{at}pku.edu.cn.
  • Author contributions: Y.Z., K.-W.H., and J.Z. designed research; Y.Z., X.G., H.C., and J.Z. performed research; B.Z., Y.P., H.L., S.M., C.G., and K.-W.H. contributed new reagents/analytic tools; Y.Z., X.C., H.C., K.-W.H., and J.Z. analyzed data; and Y.Z., X.C., K.-W.H., and J.Z. wrote the paper.

  • The authors declare no conflict of interest.

  • This article is a PNAS Direct Submission.

  • This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1809342115/-/DCSupplemental.

Published under the PNAS license.

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Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy
Yufan Zhang, Xin Chen, Bin Zheng, Xunmin Guo, Yupeng Pan, Hailong Chen, Huaifeng Li, Shixiong Min, Chao Guan, Kuo-Wei Huang, Junrong Zheng
Proceedings of the National Academy of Sciences Dec 2018, 115 (49) 12395-12400; DOI: 10.1073/pnas.1809342115

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Structural analysis of transient reaction intermediate in formic acid dehydrogenation catalysis using two-dimensional IR spectroscopy
Yufan Zhang, Xin Chen, Bin Zheng, Xunmin Guo, Yupeng Pan, Hailong Chen, Huaifeng Li, Shixiong Min, Chao Guan, Kuo-Wei Huang, Junrong Zheng
Proceedings of the National Academy of Sciences Dec 2018, 115 (49) 12395-12400; DOI: 10.1073/pnas.1809342115
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