Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen

Yoonsu Park; Sangmin Kim; Lei Tian; Hongyu Zhong; Gregory D. Scholes; Paul J. Chirik

doi:10.1038/s41557-021-00732-z

Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen

Yoonsu Park, Sangmin Kim, Lei Tian, Hongyu Zhong, Gregory D. Scholes, Paul J. Chirik

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol⁻¹. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry. [Figure not available: see fulltext.].

Original language	English
Pages (from-to)	969-976
Number of pages	8
Journal	Nature chemistry
Volume	13
Issue number	10
DOIs	https://doi.org/10.1038/s41557-021-00732-z
Publication status	Published - 2021 Oct

Bibliographical note

Funding Information:
This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Catalysis Science Program, under Award DE-SC0006498 and the Andlinger Center for Energy and the Environment (Princeton University). S.K. acknowledges a Samsung Scholarship for partial financial support. L.T. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences of the US DOE through Grant No. DE-SC0019370. G.D.S. is a CIFAR Fellow in the Bio-Inspired Energy Program. We are grateful to K. Conover (Princeton University) for assistance with photo-NMR experiments and L. Mendelsohn and D. Wang (Princeton University) for helpful discussions.

Publisher Copyright:
© 2021, The Author(s), under exclusive licence to Springer Nature Limited.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Chemical Engineering(all)

Access to Document

10.1038/s41557-021-00732-z

Cite this

@article{f8fd32bc47b74eb5a1d8fc699c095693,

title = "Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen",

abstract = "The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol−1. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry. [Figure not available: see fulltext.].",

author = "Yoonsu Park and Sangmin Kim and Lei Tian and Hongyu Zhong and Scholes, {Gregory D.} and Chirik, {Paul J.}",

note = "Funding Information: This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Catalysis Science Program, under Award DE-SC0006498 and the Andlinger Center for Energy and the Environment (Princeton University). S.K. acknowledges a Samsung Scholarship for partial financial support. L.T. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences of the US DOE through Grant No. DE-SC0019370. G.D.S. is a CIFAR Fellow in the Bio-Inspired Energy Program. We are grateful to K. Conover (Princeton University) for assistance with photo-NMR experiments and L. Mendelsohn and D. Wang (Princeton University) for helpful discussions. Publisher Copyright: {\textcopyright} 2021, The Author(s), under exclusive licence to Springer Nature Limited.",

year = "2021",

month = oct,

doi = "10.1038/s41557-021-00732-z",

language = "English",

volume = "13",

pages = "969--976",

journal = "Nature Chemistry",

issn = "1755-4330",

publisher = "Nature Publishing Group",

number = "10",

}

TY - JOUR

T1 - Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen

AU - Park, Yoonsu

AU - Kim, Sangmin

AU - Tian, Lei

AU - Zhong, Hongyu

AU - Scholes, Gregory D.

AU - Chirik, Paul J.

N1 - Funding Information: This research was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Catalysis Science Program, under Award DE-SC0006498 and the Andlinger Center for Energy and the Environment (Princeton University). S.K. acknowledges a Samsung Scholarship for partial financial support. L.T. and G.D.S. acknowledge support from the Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences of the US DOE through Grant No. DE-SC0019370. G.D.S. is a CIFAR Fellow in the Bio-Inspired Energy Program. We are grateful to K. Conover (Princeton University) for assistance with photo-NMR experiments and L. Mendelsohn and D. Wang (Princeton University) for helpful discussions. Publisher Copyright: © 2021, The Author(s), under exclusive licence to Springer Nature Limited.

PY - 2021/10

Y1 - 2021/10

N2 - The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol−1. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry. [Figure not available: see fulltext.].

AB - The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol−1. Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. Photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistry. [Figure not available: see fulltext.].

UR - http://www.scopus.com/inward/record.url?scp=85110489647&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85110489647&partnerID=8YFLogxK

U2 - 10.1038/s41557-021-00732-z

DO - 10.1038/s41557-021-00732-z

M3 - Article

C2 - 34253889

AN - SCOPUS:85110489647

SN - 1755-4330

VL - 13

SP - 969

EP - 976

JO - Nature Chemistry

JF - Nature Chemistry

IS - 10

ER -

Visible light enables catalytic formation of weak chemical bonds with molecular hydrogen

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this