Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer.
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| Title: | Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer. |
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| Authors: | Thomas, Andrew M.1, Bo-Lin Lin1, Wasinger, Erik C.2, Stack, T. Daniel P.1 stack@stanford.edu |
| Source: | Journal of the American Chemical Society. 12/18/2013, Vol. 135 Issue 50, p18912-18919. 8p. |
| Subjects: | Molecular structure of copper compounds, Isomerization kinetics, Oxidation-reduction reaction, Charge exchange, Proton transfer reaction kinetics, Copper ions |
| Abstract: | Copper thiolate/disulfide interconversions are related to the functions of several important proteins such as human Sco1, Cu–Zn superoxide dismutase (SOD1), and mammalian zinc-bonded metallothionein. The synthesis and characterization of well-defined synthetic analogues for such interconversions are challenging yet provide important insights into the mechanisms of such redox processes. Solvent-dependent redox isomerization and proton-coupled electron transfer mimicking these interconversions are observed in two structurally related dimeric μ,η²:η²-thiolato Cu(II)Cu(II) complexes by various methods, including X-ray diffraction, XAS, NMR, and UV–vis. Spectroscopic evidence shows that a solvent-dependent equilibrium exists between the dimeric μ-thiolato Cu(II)Cu(II) state and its redox isomeric μ-disulfido Cu(I)Cu(I) form. Complete formation of μ-disulfido Cu(I)Cu(I) complexes, however, only occurs after the addition of 2 equiv of protons, which promote electron transfer from thiolate to Cu(II) and formation of disulfide and Cu(I) via protonation of the coordinating ligand. Proton removal reverses this reaction. The reported unusual reductive protonation/oxidative deprotonation of the metal centers may serve as a new chemical precedent for how related proteins manage Cu ions in living organisms. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Thomas%2C+Andrew+M%2E%22">Thomas, Andrew M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Bo-Lin+Lin%22">Bo-Lin Lin</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Wasinger%2C+Erik+C%2E%22">Wasinger, Erik C.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Stack%2C+T%2E+Daniel+P%2E%22">Stack, T. Daniel P.</searchLink><relatesTo>1</relatesTo><i> stack@stanford.edu</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+the+American+Chemical+Society%22">Journal of the American Chemical Society</searchLink>. 12/18/2013, Vol. 135 Issue 50, p18912-18919. 8p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Molecular+structure+of+copper+compounds%22">Molecular structure of copper compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Isomerization+kinetics%22">Isomerization kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Charge+exchange%22">Charge exchange</searchLink><br /><searchLink fieldCode="DE" term="%22Proton+transfer+reaction+kinetics%22">Proton transfer reaction kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Copper+ions%22">Copper ions</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Copper thiolate/disulfide interconversions are related to the functions of several important proteins such as human Sco1, Cu–Zn superoxide dismutase (SOD1), and mammalian zinc-bonded metallothionein. The synthesis and characterization of well-defined synthetic analogues for such interconversions are challenging yet provide important insights into the mechanisms of such redox processes. Solvent-dependent redox isomerization and proton-coupled electron transfer mimicking these interconversions are observed in two structurally related dimeric μ,η²:η²-thiolato Cu(II)Cu(II) complexes by various methods, including X-ray diffraction, XAS, NMR, and UV–vis. Spectroscopic evidence shows that a solvent-dependent equilibrium exists between the dimeric μ-thiolato Cu(II)Cu(II) state and its redox isomeric μ-disulfido Cu(I)Cu(I) form. Complete formation of μ-disulfido Cu(I)Cu(I) complexes, however, only occurs after the addition of 2 equiv of protons, which promote electron transfer from thiolate to Cu(II) and formation of disulfide and Cu(I) via protonation of the coordinating ligand. Proton removal reverses this reaction. The reported unusual reductive protonation/oxidative deprotonation of the metal centers may serve as a new chemical precedent for how related proteins manage Cu ions in living organisms. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of the American Chemical Society is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ja409603m Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 8 StartPage: 18912 Subjects: – SubjectFull: Molecular structure of copper compounds Type: general – SubjectFull: Isomerization kinetics Type: general – SubjectFull: Oxidation-reduction reaction Type: general – SubjectFull: Charge exchange Type: general – SubjectFull: Proton transfer reaction kinetics Type: general – SubjectFull: Copper ions Type: general Titles: – TitleFull: Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Thomas, Andrew M. – PersonEntity: Name: NameFull: Bo-Lin Lin – PersonEntity: Name: NameFull: Wasinger, Erik C. – PersonEntity: Name: NameFull: Stack, T. Daniel P. IsPartOfRelationships: – BibEntity: Dates: – D: 18 M: 12 Text: 12/18/2013 Type: published Y: 2013 Identifiers: – Type: issn-print Value: 00027863 Numbering: – Type: volume Value: 135 – Type: issue Value: 50 Titles: – TitleFull: Journal of the American Chemical Society Type: main |
| ResultId | 1 |
