Toward more efficient photochemical CO2 reduction: Use of scCO2 or photogenerated hydrides

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Abstract

Rhenium(I) and ruthenium(II) complexes have been successfully used for photochemical CO2 reduction to CO or formate. However, a typical turnover frequency for such reactions is -1 and the formation of reduced species beyond CO or formate is very limited. In the case of the rhenium(I) bipyridyl tricarbonyl system, the key intermediate has been shown to decay with a first-order dependence on [CO2] to produce CO, which is the rate-determining step. The limited concentration of dissolved CO2 in organic solvents results in extremely slow CO2 reduction. To improve the reaction rate, we prepared new CO2-soluble rhenium(I) bipyridine complexes bearing fluorinated alkyl ligands and investigated their photophysical properties in CH3CN and supercritical CO2. We also investigated the properties of a metal complex with an NAD+ model ligand, [Ru(bpy)2(pbn)]2+ (bpy=2,2′-bipyridine, pbn=2-(2-pyridyl)-benzo[b]-1,5-naphthyridine), and prepared the corresponding NADH-like complex [Ru(bpy)2(pbnHH)]2+ upon MLCT excitation followed by reductive quenching. This species can be used as a renewable hydride donor. The electrochemical and photochemical properties, and the reactivity of these species toward CO2 reduction were investigated.

Original languageEnglish
Pages (from-to)2472-2482
Number of pages11
JournalCoordination Chemistry Reviews
Volume254
Issue number21-22
DOIs
Publication statusPublished - Nov 2010

Fingerprint

formic acid
Rhenium
rhenium
Carbon Monoxide
Hydrides
hydrides
formates
NAD
Bearings (structural)
Ligands
2,2'-Dipyridyl
ligands
Ruthenium
Coordination Complexes
Metal complexes
Organic solvents
ruthenium
Reaction rates
Quenching
reaction kinetics

Keywords

  • Carbon dioxide reduction
  • NADH-model ligands
  • Photocatalysis
  • Renewable hydride donors
  • Small molecule activation
  • Supercritical CO

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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title = "Toward more efficient photochemical CO2 reduction: Use of scCO2 or photogenerated hydrides",
abstract = "Rhenium(I) and ruthenium(II) complexes have been successfully used for photochemical CO2 reduction to CO or formate. However, a typical turnover frequency for such reactions is -1 and the formation of reduced species beyond CO or formate is very limited. In the case of the rhenium(I) bipyridyl tricarbonyl system, the key intermediate has been shown to decay with a first-order dependence on [CO2] to produce CO, which is the rate-determining step. The limited concentration of dissolved CO2 in organic solvents results in extremely slow CO2 reduction. To improve the reaction rate, we prepared new CO2-soluble rhenium(I) bipyridine complexes bearing fluorinated alkyl ligands and investigated their photophysical properties in CH3CN and supercritical CO2. We also investigated the properties of a metal complex with an NAD+ model ligand, [Ru(bpy)2(pbn)]2+ (bpy=2,2′-bipyridine, pbn=2-(2-pyridyl)-benzo[b]-1,5-naphthyridine), and prepared the corresponding NADH-like complex [Ru(bpy)2(pbnHH)]2+ upon MLCT excitation followed by reductive quenching. This species can be used as a renewable hydride donor. The electrochemical and photochemical properties, and the reactivity of these species toward CO2 reduction were investigated.",
keywords = "Carbon dioxide reduction, NADH-model ligands, Photocatalysis, Renewable hydride donors, Small molecule activation, Supercritical CO",
author = "Doherty, {Mark D.} and David Grills and James Muckerman and Dmitry Polyansky and Etsuko Fujita",
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T1 - Toward more efficient photochemical CO2 reduction

T2 - Use of scCO2 or photogenerated hydrides

AU - Doherty, Mark D.

AU - Grills, David

AU - Muckerman, James

AU - Polyansky, Dmitry

AU - Fujita, Etsuko

PY - 2010/11

Y1 - 2010/11

N2 - Rhenium(I) and ruthenium(II) complexes have been successfully used for photochemical CO2 reduction to CO or formate. However, a typical turnover frequency for such reactions is -1 and the formation of reduced species beyond CO or formate is very limited. In the case of the rhenium(I) bipyridyl tricarbonyl system, the key intermediate has been shown to decay with a first-order dependence on [CO2] to produce CO, which is the rate-determining step. The limited concentration of dissolved CO2 in organic solvents results in extremely slow CO2 reduction. To improve the reaction rate, we prepared new CO2-soluble rhenium(I) bipyridine complexes bearing fluorinated alkyl ligands and investigated their photophysical properties in CH3CN and supercritical CO2. We also investigated the properties of a metal complex with an NAD+ model ligand, [Ru(bpy)2(pbn)]2+ (bpy=2,2′-bipyridine, pbn=2-(2-pyridyl)-benzo[b]-1,5-naphthyridine), and prepared the corresponding NADH-like complex [Ru(bpy)2(pbnHH)]2+ upon MLCT excitation followed by reductive quenching. This species can be used as a renewable hydride donor. The electrochemical and photochemical properties, and the reactivity of these species toward CO2 reduction were investigated.

AB - Rhenium(I) and ruthenium(II) complexes have been successfully used for photochemical CO2 reduction to CO or formate. However, a typical turnover frequency for such reactions is -1 and the formation of reduced species beyond CO or formate is very limited. In the case of the rhenium(I) bipyridyl tricarbonyl system, the key intermediate has been shown to decay with a first-order dependence on [CO2] to produce CO, which is the rate-determining step. The limited concentration of dissolved CO2 in organic solvents results in extremely slow CO2 reduction. To improve the reaction rate, we prepared new CO2-soluble rhenium(I) bipyridine complexes bearing fluorinated alkyl ligands and investigated their photophysical properties in CH3CN and supercritical CO2. We also investigated the properties of a metal complex with an NAD+ model ligand, [Ru(bpy)2(pbn)]2+ (bpy=2,2′-bipyridine, pbn=2-(2-pyridyl)-benzo[b]-1,5-naphthyridine), and prepared the corresponding NADH-like complex [Ru(bpy)2(pbnHH)]2+ upon MLCT excitation followed by reductive quenching. This species can be used as a renewable hydride donor. The electrochemical and photochemical properties, and the reactivity of these species toward CO2 reduction were investigated.

KW - Carbon dioxide reduction

KW - NADH-model ligands

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KW - Renewable hydride donors

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