Deprotonation of Water/Hydroxo Ligands in Clusters Mimicking the Water Oxidizing Complex of PSII and Its Effect on the Vibrational Frequencies of Ligated Carboxylate Groups.
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| Title: | Deprotonation of Water/Hydroxo Ligands in Clusters Mimicking the Water Oxidizing Complex of PSII and Its Effect on the Vibrational Frequencies of Ligated Carboxylate Groups. |
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| Authors: | Wooi Yee Chuah1 wychuah@yahoo.com, Stranger, Rob1 Rob.Stranger@anu.edu.au, Pace, Ron J.1 Ron.Pace@anu.edu.au, Krausz, Elmars1 krausz@rsc.anu.edu.au, Frankcombe, Terry J.1,2 t.frankcombe@adfa.edu.au |
| Source: | Journal of Physical Chemistry B. Jan2016, Vol. 120 Issue 3, p377-385. 9p. |
| Subjects: | Proton transfer reactions, Ligand analysis, Water analysis, Frequencies of oscillating systems, Carboxylates |
| Abstract: | The IR absorptions of several first-shell carboxylate ligands of the water oxidizing complex (WOC) have been experimentally shown to be unaffected by oxidation state changes in the WOC during its catalytic cycle. Several model clusters that mimic the Mn4O5Ca core of the WOC in the S1 state, with electronic configurations that correspond to both the so-called "high" and "low" oxidation paradigms, were investigated. Deprotonation at W2, W1, or O3 sites was found to strongly reduce carboxylate ligand frequency shifts on oxidation of the metal cluster. The frequency shifts were smallest in neutrally charged clusters where the initial mean Mn oxidation state was +3, with W2 as an hydroxide and O5 a water. Deprotonation also reduced and balanced the oxidation energy of all clusters in successive oxidations. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry B 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: Deprotonation of Water/Hydroxo Ligands in Clusters Mimicking the Water Oxidizing Complex of PSII and Its Effect on the Vibrational Frequencies of Ligated Carboxylate Groups. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Wooi+Yee+Chuah%22">Wooi Yee Chuah</searchLink><relatesTo>1</relatesTo><i> wychuah@yahoo.com</i><br /><searchLink fieldCode="AR" term="%22Stranger%2C+Rob%22">Stranger, Rob</searchLink><relatesTo>1</relatesTo><i> Rob.Stranger@anu.edu.au</i><br /><searchLink fieldCode="AR" term="%22Pace%2C+Ron+J%2E%22">Pace, Ron J.</searchLink><relatesTo>1</relatesTo><i> Ron.Pace@anu.edu.au</i><br /><searchLink fieldCode="AR" term="%22Krausz%2C+Elmars%22">Krausz, Elmars</searchLink><relatesTo>1</relatesTo><i> krausz@rsc.anu.edu.au</i><br /><searchLink fieldCode="AR" term="%22Frankcombe%2C+Terry+J%2E%22">Frankcombe, Terry J.</searchLink><relatesTo>1,2</relatesTo><i> t.frankcombe@adfa.edu.au</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+B%22">Journal of Physical Chemistry B</searchLink>. Jan2016, Vol. 120 Issue 3, p377-385. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Proton+transfer+reactions%22">Proton transfer reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Ligand+analysis%22">Ligand analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Water+analysis%22">Water analysis</searchLink><br /><searchLink fieldCode="DE" term="%22Frequencies+of+oscillating+systems%22">Frequencies of oscillating systems</searchLink><br /><searchLink fieldCode="DE" term="%22Carboxylates%22">Carboxylates</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The IR absorptions of several first-shell carboxylate ligands of the water oxidizing complex (WOC) have been experimentally shown to be unaffected by oxidation state changes in the WOC during its catalytic cycle. Several model clusters that mimic the Mn4O5Ca core of the WOC in the S1 state, with electronic configurations that correspond to both the so-called "high" and "low" oxidation paradigms, were investigated. Deprotonation at W2, W1, or O3 sites was found to strongly reduce carboxylate ligand frequency shifts on oxidation of the metal cluster. The frequency shifts were smallest in neutrally charged clusters where the initial mean Mn oxidation state was +3, with W2 as an hydroxide and O5 a water. Deprotonation also reduced and balanced the oxidation energy of all clusters in successive oxidations. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry B 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/acs.jpcb.5b09987 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 377 Subjects: – SubjectFull: Proton transfer reactions Type: general – SubjectFull: Ligand analysis Type: general – SubjectFull: Water analysis Type: general – SubjectFull: Frequencies of oscillating systems Type: general – SubjectFull: Carboxylates Type: general Titles: – TitleFull: Deprotonation of Water/Hydroxo Ligands in Clusters Mimicking the Water Oxidizing Complex of PSII and Its Effect on the Vibrational Frequencies of Ligated Carboxylate Groups. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Wooi Yee Chuah – PersonEntity: Name: NameFull: Stranger, Rob – PersonEntity: Name: NameFull: Pace, Ron J. – PersonEntity: Name: NameFull: Krausz, Elmars – PersonEntity: Name: NameFull: Frankcombe, Terry J. IsPartOfRelationships: – BibEntity: Dates: – D: 28 M: 01 Text: Jan2016 Type: published Y: 2016 Identifiers: – Type: issn-print Value: 15206106 Numbering: – Type: volume Value: 120 – Type: issue Value: 3 Titles: – TitleFull: Journal of Physical Chemistry B Type: main |
| ResultId | 1 |
