期刊
DALTON TRANSACTIONS
卷 42, 期 23, 页码 8498-8503出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt50612f
关键词
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资金
- Air Force Office of Scientific Research through the MURI program under AFOSR Award [FA9550-10-1-0572]
- Amgen Foundation
- Amgen Scholars Program
[Re(bpy-tBu)(CO)(4)](OTf) (bpy-tBu = 4,4'-di-tert-butyl-2,2'-bipyridine, OTf = trifluoromethanesulfonate) (1) and [Re(bpy)(CO)(4)](OTf) (bpy = 2,2'-bipyridine) (2) were synthesized and studied as proposed intermediates in the electrocatalytic reduction of carbon dioxide (CO2) by Re(bpy-R)(CO)(3)X. Both compounds demonstrated increased current responses in cyclic voltammograms under CO2. Complex 1 was also characterized by X-ray crystallography. Infrared-spectroelectrochemistry (IR-SEC) of 1 and 2 indicated that upon exposure of the cationic tetracarbonyl compounds to a reducing potential, a CO ligand is labilised and [Re(bpy-R)(CO)(3)(CH3CN)](+) species are formed. This is proposed to occur via an electron-transfer-catalysed process wherein a catalytic amount of reduced species propagates a ligand exchange reaction. Addition of a catalytic amount of potassium intercalated graphite (KC8), a chemical reductant, to a solution of 1 or 2 also yielded quantitative formation of [Re(bpy-R)(CO)(3)(CH3CN)](+), which indicates that the CO loss is catalysed by electron transfer, and not the electrode itself.
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