The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation
Abstract
The reversible activation of H2 via a pathway involving metal–ligand cooperation (MLC) is proposed to be important in many transition metal catalyzed hydrogenation and dehydrogenation reactions. Nevertheless, there is a paucity of experimental information probing the mechanism of this transformation. In this paper, we present an in-depth kinetic study of the 1,2-addition of H2 via an MLC pathway to the widely used iron catalyst [(iPrPNP)FeH(CO)] (1) (iPrPNP = N(CH2CH2PiPr2)2–). We report one of the first experimental demonstrations of an enhancement in rate for the activation of H2 using protic additives, which operate as “proton shuttles”. Our results indicate that proton shuttles need to be able to both simultaneously donate and accept a proton, and the best shuttles are molecules that are strong hydrogen bond donors but sufficiently weak acids to avoid deleterious protonation of the transition metal complex. Additionally, comparison of the rate of H2 activation via an MLC pathway between 1 and two widely used ruthenium catalysts enables more general conclusions about the role of the metal, ancillary ligand, and proton shuttles in H2 activation. The results of this study provide guidance about the design of catalysts and additives to promote H2 activation via an MLC pathway.
- Authors:
-
[1];
[2];
[1]
- Yale Univ., New Haven, CT (United States)
- Univ. of Missouri, Columbia, MO (United States)
- Publication Date:
- Research Org.:
- Univ. of Missouri, Columbia, MO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1594892
- Grant/Contract Number:
- SC0018222
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 43; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Smith, Nicholas E., Bernskoetter, Wesley H., and Hazari, Nilay. The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b09062.
Smith, Nicholas E., Bernskoetter, Wesley H., & Hazari, Nilay. The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation. United States. https://doi.org/10.1021/jacs.9b09062
Smith, Nicholas E., Bernskoetter, Wesley H., and Hazari, Nilay. Wed .
"The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation". United States. https://doi.org/10.1021/jacs.9b09062. https://www.osti.gov/servlets/purl/1594892.
@article{osti_1594892,
title = {The Role of Proton Shuttles in the Reversible Activation of Hydrogen via Metal–Ligand Cooperation},
author = {Smith, Nicholas E. and Bernskoetter, Wesley H. and Hazari, Nilay},
abstractNote = {The reversible activation of H2 via a pathway involving metal–ligand cooperation (MLC) is proposed to be important in many transition metal catalyzed hydrogenation and dehydrogenation reactions. Nevertheless, there is a paucity of experimental information probing the mechanism of this transformation. In this paper, we present an in-depth kinetic study of the 1,2-addition of H2 via an MLC pathway to the widely used iron catalyst [(iPrPNP)FeH(CO)] (1) (iPrPNP = N(CH2CH2PiPr2)2–). We report one of the first experimental demonstrations of an enhancement in rate for the activation of H2 using protic additives, which operate as “proton shuttles”. Our results indicate that proton shuttles need to be able to both simultaneously donate and accept a proton, and the best shuttles are molecules that are strong hydrogen bond donors but sufficiently weak acids to avoid deleterious protonation of the transition metal complex. Additionally, comparison of the rate of H2 activation via an MLC pathway between 1 and two widely used ruthenium catalysts enables more general conclusions about the role of the metal, ancillary ligand, and proton shuttles in H2 activation. The results of this study provide guidance about the design of catalysts and additives to promote H2 activation via an MLC pathway.},
doi = {10.1021/jacs.9b09062},
journal = {Journal of the American Chemical Society},
number = 43,
volume = 141,
place = {United States},
year = {2019},
month = {10}
}
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Figures / Tables:
Figure 1: Mechanisms for H2 activation by a transition metal complex involving (a) Oxidative addition and (b) Metal-ligand cooperation (MLC).
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Works referencing / citing this record:
Dehydropolymerisation of Methylamine Borane and an N ‐Substituted Primary Amine Borane Using a PNP Fe Catalyst
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