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

129 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

@article{d66ca497fd0744708e2099c5ea526d2e,

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)",

volume = "52",

pages = "4841--4844",

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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AB - 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.

KW - EXAFS

KW - XANES

KW - homogeneous catalysis

KW - non-innocent ligands

KW - rhenium

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