Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex.
Saved in:
| Title: | Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex. |
|---|---|
| Authors: | Chiang, Linus1, Stack, T. Daniel P.1, Wasinger, Erik C.2, Shimazaki, Yuichi3, Jr.Young, Victor4, Storr, Tim5 |
| Source: | Inorganica Chimica Acta. Sep2018, Vol. 481, p151-158. 8p. |
| Subjects: | Cyclic voltammetry, Electronic structure, Phenol, Phenoxides, Electrons |
| Abstract: | The tetradentate mixed imino/amino phenoxide ligand (N-(3,5-di- tert -butylsalicylidene)-N′-(2-hydroxyl-3,5-di-tert-butylbenzyl))- trans -1,2-cyclohexanediamine (salalen) was complexed with Cu II , and the resulting Cu complex ( 2 ) was characterized by a number of experimental techniques and theoretical calculations. Two quasi-reversible redox processes for 2 , as observed by cyclic voltammetry, demonstrated the potential stability of oxidized forms, and also the increased electron-donating ability of the salalen ligand in comparison to the salen analogue. The electronic structure of the one-electron oxidized [2] + was studied in detail, and Cu K-edge X-ray Absorption Spectroscopy (XAS) measurements confirmed a Cu II -phenoxyl radical complex in solution. Resonance Raman (rR) and variable temperature 1 H NMR studies, coupled with theoretical calculations, showed that [ 2 ] + is a triplet ( S = 1) Cu II -phenoxyl radical species, with localization of the radical on the more electron-rich aminophenoxide. Attempted isolation of X-ray quality crystals of [ 2 ] + afforded [ 2 H] + , with a protonated phenol bonded to Cu II , and an additional H-bonding interaction with the SbF 6 − counterion. Stoichiometric reaction of dilute solutions of [ 2 ] + with benzyl alcohol showed that the complex reacts in a similar manner as the oxidized Cu II -salen analogue, and does not exhibit a substrate-binding pre-equilibrium as observed for the oxidized bis-aminophenoxide Cu II -salan derivative. [ABSTRACT FROM AUTHOR] |
| Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. 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 |
|---|---|
| Header | DbId: egs DbLabel: Engineering Source An: 131251962 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Chiang%2C+Linus%22">Chiang, Linus</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Stack%2C+T%2E+Daniel+P%2E%22">Stack, T. Daniel P.</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="%22Shimazaki%2C+Yuichi%22">Shimazaki, Yuichi</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Jr%2EYoung%2C+Victor%22">Jr.Young, Victor</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Storr%2C+Tim%22">Storr, Tim</searchLink><relatesTo>5</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Inorganica+Chimica+Acta%22">Inorganica Chimica Acta</searchLink>. Sep2018, Vol. 481, p151-158. 8p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Cyclic+voltammetry%22">Cyclic voltammetry</searchLink><br /><searchLink fieldCode="DE" term="%22Electronic+structure%22">Electronic structure</searchLink><br /><searchLink fieldCode="DE" term="%22Phenol%22">Phenol</searchLink><br /><searchLink fieldCode="DE" term="%22Phenoxides%22">Phenoxides</searchLink><br /><searchLink fieldCode="DE" term="%22Electrons%22">Electrons</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The tetradentate mixed imino/amino phenoxide ligand (N-(3,5-di- tert -butylsalicylidene)-N′-(2-hydroxyl-3,5-di-tert-butylbenzyl))- trans -1,2-cyclohexanediamine (salalen) was complexed with Cu II , and the resulting Cu complex ( 2 ) was characterized by a number of experimental techniques and theoretical calculations. Two quasi-reversible redox processes for 2 , as observed by cyclic voltammetry, demonstrated the potential stability of oxidized forms, and also the increased electron-donating ability of the salalen ligand in comparison to the salen analogue. The electronic structure of the one-electron oxidized [2] + was studied in detail, and Cu K-edge X-ray Absorption Spectroscopy (XAS) measurements confirmed a Cu II -phenoxyl radical complex in solution. Resonance Raman (rR) and variable temperature 1 H NMR studies, coupled with theoretical calculations, showed that [ 2 ] + is a triplet ( S = 1) Cu II -phenoxyl radical species, with localization of the radical on the more electron-rich aminophenoxide. Attempted isolation of X-ray quality crystals of [ 2 ] + afforded [ 2 H] + , with a protonated phenol bonded to Cu II , and an additional H-bonding interaction with the SbF 6 − counterion. Stoichiometric reaction of dilute solutions of [ 2 ] + with benzyl alcohol showed that the complex reacts in a similar manner as the oxidized Cu II -salen analogue, and does not exhibit a substrate-binding pre-equilibrium as observed for the oxidized bis-aminophenoxide Cu II -salan derivative. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Inorganica Chimica Acta is the property of Elsevier B.V. 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.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=131251962 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1016/j.ica.2017.09.042 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 8 StartPage: 151 Subjects: – SubjectFull: Cyclic voltammetry Type: general – SubjectFull: Electronic structure Type: general – SubjectFull: Phenol Type: general – SubjectFull: Phenoxides Type: general – SubjectFull: Electrons Type: general Titles: – TitleFull: Electronic structure and reactivity studies of a nonsymmetric one-electron oxidized CuII bis-phenoxide complex. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Chiang, Linus – PersonEntity: Name: NameFull: Stack, T. Daniel P. – PersonEntity: Name: NameFull: Wasinger, Erik C. – PersonEntity: Name: NameFull: Shimazaki, Yuichi – PersonEntity: Name: NameFull: Jr.Young, Victor – PersonEntity: Name: NameFull: Storr, Tim IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 09 Text: Sep2018 Type: published Y: 2018 Identifiers: – Type: issn-print Value: 00201693 Numbering: – Type: volume Value: 481 Titles: – TitleFull: Inorganica Chimica Acta Type: main |
| ResultId | 1 |
