The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO2 Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry

被引：114

作者：

Benson, Eric E. ^{[1
]}

Sampson, Matthew D. ^{[1
]}

Grice, Kyle A. ^{[1
]}

Smieja, Jonathan M. ^{[1
]}

Froehlich, Jesse D. ^{[1
]}

Friebel, Daniel ^{[2
]}

Keith, John A. ^{[3
]}

Carter, Emily A. ^{[3
]}

Nilsson, Anders ^{[2
]}

Kubiak, Clifford P. ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

[2] SLAC Natl Accelerator Lab, Menlo Pk, CA 94025 USA

[3] Princeton Univ, Dept Mech & Aerosp Engn, Princeton, NJ 08544 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2013年 / 52卷 / 18期

关键词：

EXAFS; homogeneous catalysis; non-innocent ligands; rhenium; XANES; CARBON-DIOXIDE; COMPLEXES; LIGANDS; DENSITY;

D O I：

10.1002/anie.201209911

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：4841 / 4844

页数：4

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