Detailed Evaluation of the Geometric and Electronic Structures of One-Electron Oxidized Group 10 (Ni, Pd, and Pt)Metal(ll)-(Disalicylidene)diamine Complexes.
Saved in:
| Title: | Detailed Evaluation of the Geometric and Electronic Structures of One-Electron Oxidized Group 10 (Ni, Pd, and Pt)Metal(ll)-(Disalicylidene)diamine Complexes. |
|---|---|
| Authors: | Shimazaki, Yuichi1, Stack, T. Daniel P.2, Storr, Tim3 yshima@mx.ibaraki.ac.jp |
| Source: | Inorganic Chemistry. 9/7/2009, Vol. 48 Issue 17, p8383-8392. 10p. |
| Subjects: | Density functionals, Electronic structure, Spectrum analysis, Chemical bonds, Physical & theoretical chemistry |
| Abstract: | The geometric and electronic structures of a series of one-electron oxidized group 10 metal salens (Ni, Pd, Pt) have been investigated in solution and in the solid state. Ni (1) and Pd (2) complexes of the tetradentate salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (H2Salcn) have been examined along with the Pt (3) complex of the salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine (H2Salen). All three oxidized compounds exist as ligand radical species in solution and in the solid state. The solid state structures of [1]+ and [3]+ exhibit a symmetric coordination sphere contraction relative to the neutral forms. By contrast, the coordination sphere of the Pd derivative [2]+ exhibits a pronounced asymmetry in the solid state. In solution, the oxidized derivatives display intense low-energy NIR transitions consistent with their classification as ligand radical compounds. Interestingly, the degree of communication between the phenolate moieties depends strongly on the central metal ion, within the Ni, Pd, and Pt series. Electrochemical measurements and UV-vis-NIR spectroscopy, in conjunction with density functional theory calculations provide insights into the degree of delocalization of the one-electron hole in these systems. The Pd complex [2]+ is the least delocalized and is best described as a borderline Class II/III intervalence complex based on the Robin-Day classification system. The Ni [1]+ and Pt [3]+ analogues are Class III (fully delocalized) intervalence compounds. Delocalization is dependent on the electronic coupling between the redox-active phenolate ligands, mediated by overlap between the formally filled metal dxz orbital and the appropriate ligand molecular orbital. The degree of coupling increases in the order Pd < Ni < Pt for the one-electron oxidized group 10 metal salens. [ABSTRACT FROM AUTHOR] |
| Copyright of Inorganic Chemistry 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 |
|---|---|
| Header | DbId: egs DbLabel: Engineering Source An: 44319730 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
| IllustrationInfo | |
| Items | – Name: Title Label: Title Group: Ti Data: Detailed Evaluation of the Geometric and Electronic Structures of One-Electron Oxidized Group 10 (Ni, Pd, and Pt)Metal(ll)-(Disalicylidene)diamine Complexes. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Shimazaki%2C+Yuichi%22">Shimazaki, Yuichi</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Stack%2C+T%2E+Daniel+P%2E%22">Stack, T. Daniel P.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Storr%2C+Tim%22">Storr, Tim</searchLink><relatesTo>3</relatesTo><i> yshima@mx.ibaraki.ac.jp</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 9/7/2009, Vol. 48 Issue 17, p8383-8392. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink><br /><searchLink fieldCode="DE" term="%22Electronic+structure%22">Electronic structure</searchLink><br /><searchLink fieldCode="DE" term="%22Spectrum+analysis%22">Spectrum analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+bonds%22">Chemical bonds</searchLink><br /><searchLink fieldCode="DE" term="%22Physical+%26+theoretical+chemistry%22">Physical & theoretical chemistry</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The geometric and electronic structures of a series of one-electron oxidized group 10 metal salens (Ni, Pd, Pt) have been investigated in solution and in the solid state. Ni (1) and Pd (2) complexes of the tetradentate salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine (H2Salcn) have been examined along with the Pt (3) complex of the salen ligand N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine (H2Salen). All three oxidized compounds exist as ligand radical species in solution and in the solid state. The solid state structures of [1]+ and [3]+ exhibit a symmetric coordination sphere contraction relative to the neutral forms. By contrast, the coordination sphere of the Pd derivative [2]+ exhibits a pronounced asymmetry in the solid state. In solution, the oxidized derivatives display intense low-energy NIR transitions consistent with their classification as ligand radical compounds. Interestingly, the degree of communication between the phenolate moieties depends strongly on the central metal ion, within the Ni, Pd, and Pt series. Electrochemical measurements and UV-vis-NIR spectroscopy, in conjunction with density functional theory calculations provide insights into the degree of delocalization of the one-electron hole in these systems. The Pd complex [2]+ is the least delocalized and is best described as a borderline Class II/III intervalence complex based on the Robin-Day classification system. The Ni [1]+ and Pt [3]+ analogues are Class III (fully delocalized) intervalence compounds. Delocalization is dependent on the electronic coupling between the redox-active phenolate ligands, mediated by overlap between the formally filled metal dxz orbital and the appropriate ligand molecular orbital. The degree of coupling increases in the order Pd < Ni < Pt for the one-electron oxidized group 10 metal salens. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Inorganic Chemistry 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.) |
| PLink | https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=44319730 |
| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ic901003q Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 8383 Subjects: – SubjectFull: Density functionals Type: general – SubjectFull: Electronic structure Type: general – SubjectFull: Spectrum analysis Type: general – SubjectFull: Chemical bonds Type: general – SubjectFull: Physical & theoretical chemistry Type: general Titles: – TitleFull: Detailed Evaluation of the Geometric and Electronic Structures of One-Electron Oxidized Group 10 (Ni, Pd, and Pt)Metal(ll)-(Disalicylidene)diamine Complexes. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Shimazaki, Yuichi – PersonEntity: Name: NameFull: Stack, T. Daniel P. – PersonEntity: Name: NameFull: Storr, Tim IsPartOfRelationships: – BibEntity: Dates: – D: 07 M: 09 Text: 9/7/2009 Type: published Y: 2009 Identifiers: – Type: issn-print Value: 00201669 Numbering: – Type: volume Value: 48 – Type: issue Value: 17 Titles: – TitleFull: Inorganic Chemistry Type: main |
| ResultId | 1 |
