Involvement of a binuclear species with the Re-C(O)O-Re moiety in CO 2 reduction catalyzed by tricarbonyl rhenium(I) complexes with diimine ligands

Strikingly slow formation of the Re-Re and Re-C(O)O-re species from Re(dmb)(CO)3S (dmb = 4,4′-dimethyl-2,2′-bipyridine, S = solvent)

Yukiko Hayashi, Shouichi Kita, Bruce S. Brunschwig, Etsuko Fujita

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215 Citations (Scopus)

Abstract

Excited-state properties of fac-[Re(dmb)(CO)3(CH 3CN)]PF6, [Re(dmb)(CO)3]2 (where dmb = 4,4′-dimethyl-2,2′-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)3S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)-(CO) 3(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)3]2. In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)3S dimerizes slowly in THF, kd = 40 ± 5 M-1 s-1. This rate constant is much smaller than those of other organometallic radicals which are typically 109 M-1 s-1. The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K ≈ 10 -4). The reaction of Re(dmb)(CO)3S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO) 3]2 in the presence of CO2 produces CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO) 3(dmb)Re-CO(O)-Re(dmb)(CO)3 is identified as an intermediate. Both [Re(dmb)(CO)3]2(OCO2) and Re(dmb)(CO)3(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.

Original languageEnglish
Pages (from-to)11976-11987
Number of pages12
JournalJournal of the American Chemical Society
Volume125
Issue number39
DOIs
Publication statusPublished - Oct 1 2003

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Rhenium
Carbon Monoxide
Excited states
Monomers
Ligands
Dimerization
Electrons
Photolysis
Organometallics
Metals
Ultraviolet spectroscopy
Dimers
Ground state
Quenching
Rate constants
Oxidation
Fourier Transform Infrared Spectroscopy

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{7857a9cdb9214be999088a5cd6fb6e15,
title = "Involvement of a binuclear species with the Re-C(O)O-Re moiety in CO 2 reduction catalyzed by tricarbonyl rhenium(I) complexes with diimine ligands: Strikingly slow formation of the Re-Re and Re-C(O)O-re species from Re(dmb)(CO)3S (dmb = 4,4′-dimethyl-2,2′-bipyridine, S = solvent)",
abstract = "Excited-state properties of fac-[Re(dmb)(CO)3(CH 3CN)]PF6, [Re(dmb)(CO)3]2 (where dmb = 4,4′-dimethyl-2,2′-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)3S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)-(CO) 3(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)3]2. In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)3S dimerizes slowly in THF, kd = 40 ± 5 M-1 s-1. This rate constant is much smaller than those of other organometallic radicals which are typically 109 M-1 s-1. The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K ≈ 10 -4). The reaction of Re(dmb)(CO)3S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO) 3]2 in the presence of CO2 produces CO with a 25-50{\%} yield based on [Re]. A CO2 bridged dimer, (CO) 3(dmb)Re-CO(O)-Re(dmb)(CO)3 is identified as an intermediate. Both [Re(dmb)(CO)3]2(OCO2) and Re(dmb)(CO)3(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.",
author = "Yukiko Hayashi and Shouichi Kita and Brunschwig, {Bruce S.} and Etsuko Fujita",
year = "2003",
month = "10",
day = "1",
doi = "10.1021/ja035960a",
language = "English",
volume = "125",
pages = "11976--11987",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Involvement of a binuclear species with the Re-C(O)O-Re moiety in CO 2 reduction catalyzed by tricarbonyl rhenium(I) complexes with diimine ligands

T2 - Strikingly slow formation of the Re-Re and Re-C(O)O-re species from Re(dmb)(CO)3S (dmb = 4,4′-dimethyl-2,2′-bipyridine, S = solvent)

AU - Hayashi, Yukiko

AU - Kita, Shouichi

AU - Brunschwig, Bruce S.

AU - Fujita, Etsuko

PY - 2003/10/1

Y1 - 2003/10/1

N2 - Excited-state properties of fac-[Re(dmb)(CO)3(CH 3CN)]PF6, [Re(dmb)(CO)3]2 (where dmb = 4,4′-dimethyl-2,2′-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)3S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)-(CO) 3(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)3]2. In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)3S dimerizes slowly in THF, kd = 40 ± 5 M-1 s-1. This rate constant is much smaller than those of other organometallic radicals which are typically 109 M-1 s-1. The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K ≈ 10 -4). The reaction of Re(dmb)(CO)3S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO) 3]2 in the presence of CO2 produces CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO) 3(dmb)Re-CO(O)-Re(dmb)(CO)3 is identified as an intermediate. Both [Re(dmb)(CO)3]2(OCO2) and Re(dmb)(CO)3(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.

AB - Excited-state properties of fac-[Re(dmb)(CO)3(CH 3CN)]PF6, [Re(dmb)(CO)3]2 (where dmb = 4,4′-dimethyl-2,2′-bipyridine), and other tricarbonyl rhenium(I) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)3S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)-(CO) 3(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)3]2. In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)3S dimerizes slowly in THF, kd = 40 ± 5 M-1 s-1. This rate constant is much smaller than those of other organometallic radicals which are typically 109 M-1 s-1. The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K ≈ 10 -4). The reaction of Re(dmb)(CO)3S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO) 3]2 in the presence of CO2 produces CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO) 3(dmb)Re-CO(O)-Re(dmb)(CO)3 is identified as an intermediate. Both [Re(dmb)(CO)3]2(OCO2) and Re(dmb)(CO)3(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.

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