Ligand tuning effects upon the multielectron reduction and single-electron oxidation of (bi)pyridyl complexes of cis- and trans-dioxorhenium(V): Redox thermodynamics, preliminary electrochemical kinetics, and charge-transfer absorption spectroscopy

M. S. Ram, Lisa M. Jones, Howard J. Ward, Ying Hsiow Wong, Christopher S. Johnson, P. Subramanian, Joseph T Hupp

Research output: Contribution to journalArticle

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Abstract

The effects of ligand substituents upon the electrochemistry and charge-transfer absorption spectroscopy of complexes of the type trans-(O)2Rev(py-X)4+ (py-X is a substituted pyridine) and cis-(O)2Rev(bpy-Y2)(py-X)2 + (bpy-Y2 is a doubly substituted 2,2′-bipyridine ligand) have been examined. Both series of complexes undergo a simple one-electron oxidation, but the Re(VI/V) potentials (Ef) are roughly 600 mV higher for the trans series compared with the cis. For both series, (bi)pyridyl substituents exert large effects: Ef(VI/V) increases by as much as several hundred millivolts upon replacement of electron-withdrawing substituents by electron-donating groups. Reduction of Re(V) is more complex. For the cis series, and a portion of the trans, it occurs by a two-electron process followed by a one-electron step. For some of the trans species, however, a three-electron reduction (to Re(II)) is seen. Furthermore the reductive reactions are pH dependent, indicating the uptake of protons (and oxo to hydroxo or aqua ligand conversion) span Re(III) or Re(II) formation. A surprising finding in view of the Re(VI/V) results is that Ef(V/III) is essentially independent of ligand composition for both the trans and cis series. A careful consideration of substituent effects for cis-(OH)2ReIII(bpy-Y2)(py-X)2 + reduction, which displays both pH-dependent (low and intermediate pH's) and pH-independent (high pH) behavior, suggests an explanation: electron-donating substituents evidently function simultaneously to decrease the affinity of the lower oxidation state for electrons (thereby making Ef more negative) while increasing the affinity for protons (thereby making Ef more positive), resulting in only a small net substituent effect. The electron/proton compensation effect appears also to be operative in the electrochemical kinetics of reduction of trans-(O)2Re(py-X)4+. Preliminary experiments show that, at Ef, the two-electron reduction is controlled by the rate of the Re(IV) to Re(III) step and that this step is preceded by a single protonation step. Qualitative rate comparisons, based on cyclic voltammetry peak separation measurements, reveal significant ligand substituent effects. There is no systematic dependence, however, of rate upon ligand electron-withdrawing or -donating character. The lack of correlation is interpreted in terms of compensating "electron demand" and "proton demand" effects in the overall two-electron, two-proton kinetic process. Studies of electronic absorption reveal complex correlations between metal-to-ligand charge transfer (MLCT) energies and Ef(VI/V) for both the cis and the trans series. For the cis series, the charge-transfer absorptions are assigned as Re(V)-to-pyridine (higher energy) and Re(V)-to-bipyridine (lower energy) on the basis of resonance Raman enhancement effects. The effects of solvent on MLCT energies and Re(VI/V) potentials are described in the Appendix. An empirical correlation between both quantities and the so-called solvent acceptor number is found. The correlations are tentatively interpreted in terms of the metal oxidation-state dependence of specific interactions between comparatively electron-rich oxo ligands and electron-deficient solvent functionalities.

Original languageEnglish
Pages (from-to)2928-2938
Number of pages11
JournalInorganic Chemistry
Volume30
Issue number14
Publication statusPublished - 1991

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Absorption spectroscopy
Charge transfer
absorption spectroscopy
Tuning
tuning
charge transfer
Thermodynamics
Ligands
Oxidation
thermodynamics
ligands
oxidation
Kinetics
Electrons
kinetics
electrons
Protons
protons
Metals
Oxidation-Reduction

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Ligand tuning effects upon the multielectron reduction and single-electron oxidation of (bi)pyridyl complexes of cis- and trans-dioxorhenium(V) : Redox thermodynamics, preliminary electrochemical kinetics, and charge-transfer absorption spectroscopy. / Ram, M. S.; Jones, Lisa M.; Ward, Howard J.; Wong, Ying Hsiow; Johnson, Christopher S.; Subramanian, P.; Hupp, Joseph T.

In: Inorganic Chemistry, Vol. 30, No. 14, 1991, p. 2928-2938.

Research output: Contribution to journalArticle

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title = "Ligand tuning effects upon the multielectron reduction and single-electron oxidation of (bi)pyridyl complexes of cis- and trans-dioxorhenium(V): Redox thermodynamics, preliminary electrochemical kinetics, and charge-transfer absorption spectroscopy",
abstract = "The effects of ligand substituents upon the electrochemistry and charge-transfer absorption spectroscopy of complexes of the type trans-(O)2Rev(py-X)4+ (py-X is a substituted pyridine) and cis-(O)2Rev(bpy-Y2)(py-X)2 + (bpy-Y2 is a doubly substituted 2,2′-bipyridine ligand) have been examined. Both series of complexes undergo a simple one-electron oxidation, but the Re(VI/V) potentials (Ef) are roughly 600 mV higher for the trans series compared with the cis. For both series, (bi)pyridyl substituents exert large effects: Ef(VI/V) increases by as much as several hundred millivolts upon replacement of electron-withdrawing substituents by electron-donating groups. Reduction of Re(V) is more complex. For the cis series, and a portion of the trans, it occurs by a two-electron process followed by a one-electron step. For some of the trans species, however, a three-electron reduction (to Re(II)) is seen. Furthermore the reductive reactions are pH dependent, indicating the uptake of protons (and oxo to hydroxo or aqua ligand conversion) span Re(III) or Re(II) formation. A surprising finding in view of the Re(VI/V) results is that Ef(V/III) is essentially independent of ligand composition for both the trans and cis series. A careful consideration of substituent effects for cis-(OH)2ReIII(bpy-Y2)(py-X)2 + reduction, which displays both pH-dependent (low and intermediate pH's) and pH-independent (high pH) behavior, suggests an explanation: electron-donating substituents evidently function simultaneously to decrease the affinity of the lower oxidation state for electrons (thereby making Ef more negative) while increasing the affinity for protons (thereby making Ef more positive), resulting in only a small net substituent effect. The electron/proton compensation effect appears also to be operative in the electrochemical kinetics of reduction of trans-(O)2Re(py-X)4+. Preliminary experiments show that, at Ef, the two-electron reduction is controlled by the rate of the Re(IV) to Re(III) step and that this step is preceded by a single protonation step. Qualitative rate comparisons, based on cyclic voltammetry peak separation measurements, reveal significant ligand substituent effects. There is no systematic dependence, however, of rate upon ligand electron-withdrawing or -donating character. The lack of correlation is interpreted in terms of compensating {"}electron demand{"} and {"}proton demand{"} effects in the overall two-electron, two-proton kinetic process. Studies of electronic absorption reveal complex correlations between metal-to-ligand charge transfer (MLCT) energies and Ef(VI/V) for both the cis and the trans series. For the cis series, the charge-transfer absorptions are assigned as Re(V)-to-pyridine (higher energy) and Re(V)-to-bipyridine (lower energy) on the basis of resonance Raman enhancement effects. The effects of solvent on MLCT energies and Re(VI/V) potentials are described in the Appendix. An empirical correlation between both quantities and the so-called solvent acceptor number is found. The correlations are tentatively interpreted in terms of the metal oxidation-state dependence of specific interactions between comparatively electron-rich oxo ligands and electron-deficient solvent functionalities.",
author = "Ram, {M. S.} and Jones, {Lisa M.} and Ward, {Howard J.} and Wong, {Ying Hsiow} and Johnson, {Christopher S.} and P. Subramanian and Hupp, {Joseph T}",
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TY - JOUR

T1 - Ligand tuning effects upon the multielectron reduction and single-electron oxidation of (bi)pyridyl complexes of cis- and trans-dioxorhenium(V)

T2 - Redox thermodynamics, preliminary electrochemical kinetics, and charge-transfer absorption spectroscopy

AU - Ram, M. S.

AU - Jones, Lisa M.

AU - Ward, Howard J.

AU - Wong, Ying Hsiow

AU - Johnson, Christopher S.

AU - Subramanian, P.

AU - Hupp, Joseph T

PY - 1991

Y1 - 1991

N2 - The effects of ligand substituents upon the electrochemistry and charge-transfer absorption spectroscopy of complexes of the type trans-(O)2Rev(py-X)4+ (py-X is a substituted pyridine) and cis-(O)2Rev(bpy-Y2)(py-X)2 + (bpy-Y2 is a doubly substituted 2,2′-bipyridine ligand) have been examined. Both series of complexes undergo a simple one-electron oxidation, but the Re(VI/V) potentials (Ef) are roughly 600 mV higher for the trans series compared with the cis. For both series, (bi)pyridyl substituents exert large effects: Ef(VI/V) increases by as much as several hundred millivolts upon replacement of electron-withdrawing substituents by electron-donating groups. Reduction of Re(V) is more complex. For the cis series, and a portion of the trans, it occurs by a two-electron process followed by a one-electron step. For some of the trans species, however, a three-electron reduction (to Re(II)) is seen. Furthermore the reductive reactions are pH dependent, indicating the uptake of protons (and oxo to hydroxo or aqua ligand conversion) span Re(III) or Re(II) formation. A surprising finding in view of the Re(VI/V) results is that Ef(V/III) is essentially independent of ligand composition for both the trans and cis series. A careful consideration of substituent effects for cis-(OH)2ReIII(bpy-Y2)(py-X)2 + reduction, which displays both pH-dependent (low and intermediate pH's) and pH-independent (high pH) behavior, suggests an explanation: electron-donating substituents evidently function simultaneously to decrease the affinity of the lower oxidation state for electrons (thereby making Ef more negative) while increasing the affinity for protons (thereby making Ef more positive), resulting in only a small net substituent effect. The electron/proton compensation effect appears also to be operative in the electrochemical kinetics of reduction of trans-(O)2Re(py-X)4+. Preliminary experiments show that, at Ef, the two-electron reduction is controlled by the rate of the Re(IV) to Re(III) step and that this step is preceded by a single protonation step. Qualitative rate comparisons, based on cyclic voltammetry peak separation measurements, reveal significant ligand substituent effects. There is no systematic dependence, however, of rate upon ligand electron-withdrawing or -donating character. The lack of correlation is interpreted in terms of compensating "electron demand" and "proton demand" effects in the overall two-electron, two-proton kinetic process. Studies of electronic absorption reveal complex correlations between metal-to-ligand charge transfer (MLCT) energies and Ef(VI/V) for both the cis and the trans series. For the cis series, the charge-transfer absorptions are assigned as Re(V)-to-pyridine (higher energy) and Re(V)-to-bipyridine (lower energy) on the basis of resonance Raman enhancement effects. The effects of solvent on MLCT energies and Re(VI/V) potentials are described in the Appendix. An empirical correlation between both quantities and the so-called solvent acceptor number is found. The correlations are tentatively interpreted in terms of the metal oxidation-state dependence of specific interactions between comparatively electron-rich oxo ligands and electron-deficient solvent functionalities.

AB - The effects of ligand substituents upon the electrochemistry and charge-transfer absorption spectroscopy of complexes of the type trans-(O)2Rev(py-X)4+ (py-X is a substituted pyridine) and cis-(O)2Rev(bpy-Y2)(py-X)2 + (bpy-Y2 is a doubly substituted 2,2′-bipyridine ligand) have been examined. Both series of complexes undergo a simple one-electron oxidation, but the Re(VI/V) potentials (Ef) are roughly 600 mV higher for the trans series compared with the cis. For both series, (bi)pyridyl substituents exert large effects: Ef(VI/V) increases by as much as several hundred millivolts upon replacement of electron-withdrawing substituents by electron-donating groups. Reduction of Re(V) is more complex. For the cis series, and a portion of the trans, it occurs by a two-electron process followed by a one-electron step. For some of the trans species, however, a three-electron reduction (to Re(II)) is seen. Furthermore the reductive reactions are pH dependent, indicating the uptake of protons (and oxo to hydroxo or aqua ligand conversion) span Re(III) or Re(II) formation. A surprising finding in view of the Re(VI/V) results is that Ef(V/III) is essentially independent of ligand composition for both the trans and cis series. A careful consideration of substituent effects for cis-(OH)2ReIII(bpy-Y2)(py-X)2 + reduction, which displays both pH-dependent (low and intermediate pH's) and pH-independent (high pH) behavior, suggests an explanation: electron-donating substituents evidently function simultaneously to decrease the affinity of the lower oxidation state for electrons (thereby making Ef more negative) while increasing the affinity for protons (thereby making Ef more positive), resulting in only a small net substituent effect. The electron/proton compensation effect appears also to be operative in the electrochemical kinetics of reduction of trans-(O)2Re(py-X)4+. Preliminary experiments show that, at Ef, the two-electron reduction is controlled by the rate of the Re(IV) to Re(III) step and that this step is preceded by a single protonation step. Qualitative rate comparisons, based on cyclic voltammetry peak separation measurements, reveal significant ligand substituent effects. There is no systematic dependence, however, of rate upon ligand electron-withdrawing or -donating character. The lack of correlation is interpreted in terms of compensating "electron demand" and "proton demand" effects in the overall two-electron, two-proton kinetic process. Studies of electronic absorption reveal complex correlations between metal-to-ligand charge transfer (MLCT) energies and Ef(VI/V) for both the cis and the trans series. For the cis series, the charge-transfer absorptions are assigned as Re(V)-to-pyridine (higher energy) and Re(V)-to-bipyridine (lower energy) on the basis of resonance Raman enhancement effects. The effects of solvent on MLCT energies and Re(VI/V) potentials are described in the Appendix. An empirical correlation between both quantities and the so-called solvent acceptor number is found. The correlations are tentatively interpreted in terms of the metal oxidation-state dependence of specific interactions between comparatively electron-rich oxo ligands and electron-deficient solvent functionalities.

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