The electronic states of rhenium bipyridyl electrocatalysts for CO 2 reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry

Eric E. Benson; Matthew D. Sampson; Kyle A. Grice; Jonathan M. Smieja; Jesse D. Froehlich; Daniel Friebel; John A. Keith; Emily A. Carter; Anders Nilsson; Clifford P. Kubiak

doi:10.1002/anie.201209911

The electronic states of rhenium bipyridyl electrocatalysts for CO ₂ reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry

Eric E. Benson, Matthew D. Sampson, Kyle A. Grice, Jonathan M. Smieja, Jesse D. Froehlich, Daniel Friebel, John A. Keith, Emily A. Carter, Anders Nilsson, Clifford P. Kubiak

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

126 Scopus citations

Abstract

Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO₂, but not H⁺? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO) ₃]^- and [Re(bpy-tBu)(CO)₃]^- is not stored in a localized Re 5d state, but rather in the bipyridine ligand. The active states of this family of catalysts possess formally Re⁰ metal centers with singly reduced bipyridine ligands.

Original language	English (US)
Pages (from-to)	4841-4844
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	52
Issue number	18
DOIs	https://doi.org/10.1002/anie.201209911
State	Published - Apr 26 2013

All Science Journal Classification (ASJC) codes

General Chemistry
Catalysis

Keywords

EXAFS
XANES
homogeneous catalysis
non-innocent ligands
rhenium

Access to Document

10.1002/anie.201209911

Cite this

Benson, E. E., Sampson, M. D., Grice, K. A., Smieja, J. M., Froehlich, J. D., Friebel, D., Keith, J. A., Carter, E. A., Nilsson, A., & Kubiak, C. P. (2013). The electronic states of rhenium bipyridyl electrocatalysts for CO ₂ reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry. Angewandte Chemie - International Edition, 52(18), 4841-4844. https://doi.org/10.1002/anie.201209911

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title = "The electronic states of rhenium bipyridyl electrocatalysts for CO 2 reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry",

abstract = "Where are the electrons that allow a highly reduced rhenium bipyridyl catalyst to attack CO2, but not H+? XAS and computational quantum chemistry indicate that the negative charge in [Re(bpy)(CO) 3]- and [Re(bpy-tBu)(CO)3]- is not stored in a localized Re 5d state, but rather in the bipyridine ligand. The active states of this family of catalysts possess formally Re0 metal centers with singly reduced bipyridine ligands.",

keywords = "EXAFS, XANES, homogeneous catalysis, non-innocent ligands, rhenium",

author = "Benson, \{Eric E.\} and Sampson, \{Matthew D.\} and Grice, \{Kyle A.\} and Smieja, \{Jonathan M.\} and Froehlich, \{Jesse D.\} and Daniel Friebel and Keith, \{John A.\} and Carter, \{Emily A.\} and Anders Nilsson and Kubiak, \{Clifford P.\}",

year = "2013",

month = apr,

day = "26",

doi = "10.1002/anie.201209911",

language = "English (US)",

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journal = "Angewandte Chemie - International Edition",

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Benson, EE, Sampson, MD, Grice, KA, Smieja, JM, Froehlich, JD, Friebel, D, Keith, JA, Carter, EA, Nilsson, A & Kubiak, CP 2013, 'The electronic states of rhenium bipyridyl electrocatalysts for CO ₂ reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry', Angewandte Chemie - International Edition, vol. 52, no. 18, pp. 4841-4844. https://doi.org/10.1002/anie.201209911

The electronic states of rhenium bipyridyl electrocatalysts for CO ₂ reduction as revealed by X-ray absorption spectroscopy and computational quantum chemistry. / Benson, Eric E.; Sampson, Matthew D.; Grice, Kyle A. et al.
In: Angewandte Chemie - International Edition, Vol. 52, No. 18, 26.04.2013, p. 4841-4844.

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

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AU - Benson, Eric E.

AU - Sampson, Matthew D.

AU - Grice, Kyle A.

AU - Smieja, Jonathan M.

AU - Froehlich, Jesse D.

AU - Friebel, Daniel

AU - Keith, John A.

AU - Carter, Emily A.

AU - Nilsson, Anders

AU - Kubiak, Clifford P.

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KW - XANES

KW - homogeneous catalysis

KW - non-innocent ligands

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