Electrochemistry of carbidopentaruthenium C60 complexes and related clusters

Audrey J. Babcock, Jinghong Li, Kwangyeol Lee, John R. Shapley

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The electrochemical behavior of the face-coordinated C60-carbidopentaruthenium cluster complexes Ru5C(CO)11(PPh332 22-C60 (1) Ru5C(CO)10(μ-η11-dppf)( μ3222-C60 ) (2) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), and PtRu5C(CO)112-dppe)(μ3- η222-C60) (3) (dppe = 1,2-bis(diphenylphosphino)ethane) has been examined by cyclic voltammetry, rotating disk electrode voltammetry, and differential pulse voltammetry methods. The behavior of compounds Ru5C(CO)15 (4), Ru5C(CO)14(PPh3) (5), Ru5C(CO)13(μ-η11-dppf) (6), PtRu5C(CO)16 (7), and PtRu5C(CO)142-dppe) (8) was studied also for comparison. For both 1 and 3, the voltammetric scans show an initial irreversible two-electron reduction feature, followed by three quasi-reversible, one-electron reductions of the C60 ligand. In contrast, similar scans for 2 indicate an initial quasi-reversible, one-electron reduction of the C60 ligand that is dynamically coupled with a second one-electron, irreversible reduction. Stepwise reduction of the C60 ligand proceeds at more negative potentials. Interpretation of the electrochemical behavior of compounds 1-8 has been enhanced by studying their chemical reduction with cobaltocene. In all cases uptake of two electrons results in irreversible loss of a CO ligand from the cluster, and the resulting dianionic complexes have been characterized by their IR (νCO) spectra.

Original languageEnglish
Pages (from-to)3940-3946
Number of pages7
JournalOrganometallics
Volume21
Issue number19
DOIs
Publication statusPublished - 2002 Sep 16
Externally publishedYes

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Electrochemistry
electrochemistry
ligands
Electrons
Ligands
electrons
Voltammetry
complex compounds
rotating disks
ethane
Rotating disks
Cyclic voltammetry
electrodes
Electrodes
pulses

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Electrochemistry of carbidopentaruthenium C60 complexes and related clusters. / Babcock, Audrey J.; Li, Jinghong; Lee, Kwangyeol; Shapley, John R.

In: Organometallics, Vol. 21, No. 19, 16.09.2002, p. 3940-3946.

Research output: Contribution to journalArticle

Babcock, Audrey J. ; Li, Jinghong ; Lee, Kwangyeol ; Shapley, John R. / Electrochemistry of carbidopentaruthenium C60 complexes and related clusters. In: Organometallics. 2002 ; Vol. 21, No. 19. pp. 3940-3946.
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title = "Electrochemistry of carbidopentaruthenium C60 complexes and related clusters",
abstract = "The electrochemical behavior of the face-coordinated C60-carbidopentaruthenium cluster complexes Ru5C(CO)11(PPh3(μ3-η2 ,η2,η2-C60 (1) Ru5C(CO)10(μ-η1,η1-dppf)( μ3-η2,η2,η2-C60 ) (2) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), and PtRu5C(CO)11(η2-dppe)(μ3- η2,η2,η2-C60) (3) (dppe = 1,2-bis(diphenylphosphino)ethane) has been examined by cyclic voltammetry, rotating disk electrode voltammetry, and differential pulse voltammetry methods. The behavior of compounds Ru5C(CO)15 (4), Ru5C(CO)14(PPh3) (5), Ru5C(CO)13(μ-η1,η1-dppf) (6), PtRu5C(CO)16 (7), and PtRu5C(CO)14(η2-dppe) (8) was studied also for comparison. For both 1 and 3, the voltammetric scans show an initial irreversible two-electron reduction feature, followed by three quasi-reversible, one-electron reductions of the C60 ligand. In contrast, similar scans for 2 indicate an initial quasi-reversible, one-electron reduction of the C60 ligand that is dynamically coupled with a second one-electron, irreversible reduction. Stepwise reduction of the C60 ligand proceeds at more negative potentials. Interpretation of the electrochemical behavior of compounds 1-8 has been enhanced by studying their chemical reduction with cobaltocene. In all cases uptake of two electrons results in irreversible loss of a CO ligand from the cluster, and the resulting dianionic complexes have been characterized by their IR (νCO) spectra.",
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N2 - The electrochemical behavior of the face-coordinated C60-carbidopentaruthenium cluster complexes Ru5C(CO)11(PPh3(μ3-η2 ,η2,η2-C60 (1) Ru5C(CO)10(μ-η1,η1-dppf)( μ3-η2,η2,η2-C60 ) (2) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), and PtRu5C(CO)11(η2-dppe)(μ3- η2,η2,η2-C60) (3) (dppe = 1,2-bis(diphenylphosphino)ethane) has been examined by cyclic voltammetry, rotating disk electrode voltammetry, and differential pulse voltammetry methods. The behavior of compounds Ru5C(CO)15 (4), Ru5C(CO)14(PPh3) (5), Ru5C(CO)13(μ-η1,η1-dppf) (6), PtRu5C(CO)16 (7), and PtRu5C(CO)14(η2-dppe) (8) was studied also for comparison. For both 1 and 3, the voltammetric scans show an initial irreversible two-electron reduction feature, followed by three quasi-reversible, one-electron reductions of the C60 ligand. In contrast, similar scans for 2 indicate an initial quasi-reversible, one-electron reduction of the C60 ligand that is dynamically coupled with a second one-electron, irreversible reduction. Stepwise reduction of the C60 ligand proceeds at more negative potentials. Interpretation of the electrochemical behavior of compounds 1-8 has been enhanced by studying their chemical reduction with cobaltocene. In all cases uptake of two electrons results in irreversible loss of a CO ligand from the cluster, and the resulting dianionic complexes have been characterized by their IR (νCO) spectra.

AB - The electrochemical behavior of the face-coordinated C60-carbidopentaruthenium cluster complexes Ru5C(CO)11(PPh3(μ3-η2 ,η2,η2-C60 (1) Ru5C(CO)10(μ-η1,η1-dppf)( μ3-η2,η2,η2-C60 ) (2) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), and PtRu5C(CO)11(η2-dppe)(μ3- η2,η2,η2-C60) (3) (dppe = 1,2-bis(diphenylphosphino)ethane) has been examined by cyclic voltammetry, rotating disk electrode voltammetry, and differential pulse voltammetry methods. The behavior of compounds Ru5C(CO)15 (4), Ru5C(CO)14(PPh3) (5), Ru5C(CO)13(μ-η1,η1-dppf) (6), PtRu5C(CO)16 (7), and PtRu5C(CO)14(η2-dppe) (8) was studied also for comparison. For both 1 and 3, the voltammetric scans show an initial irreversible two-electron reduction feature, followed by three quasi-reversible, one-electron reductions of the C60 ligand. In contrast, similar scans for 2 indicate an initial quasi-reversible, one-electron reduction of the C60 ligand that is dynamically coupled with a second one-electron, irreversible reduction. Stepwise reduction of the C60 ligand proceeds at more negative potentials. Interpretation of the electrochemical behavior of compounds 1-8 has been enhanced by studying their chemical reduction with cobaltocene. In all cases uptake of two electrons results in irreversible loss of a CO ligand from the cluster, and the resulting dianionic complexes have been characterized by their IR (νCO) spectra.

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