Elucidating the catalytic mechanisms of O2 generation by [Mn2(µ-O)2(terpy)2(OH2)2]3+ using DFT calculations: a focus on ClO- as oxidant.
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| Title: | Elucidating the catalytic mechanisms of O |
|---|---|
| Authors: | Ariafard, Alireza1 Alireza.Ariafard@anu.edu.au, Longhurst, Matthew2, Swiegers, Gerhard F.2, Stranger, Robert1 |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. 5/7/2024, Vol. 53 Issue 17, p7580-7589. 10p. |
| Subjects: | Oxidizing agents, Activation energy, Oxidation states |
| Abstract: | The experimentally reported Mn(IV)Mn(III) complex [Mn2(µ-O)2(terpy)2(OH2)2]3+ has been observed catalyzing O2 generation with oxidants like ClO- and HSO5-. Previous mechanistic studies primarily focused onO2 generation with HSO5-, concluding that Mn(IV)Mn(III) acts as a catalyst, generating a Mn(IV)Mn(IV)-oxyl species as a key intermediate responsible for O-O bond formation. This computational study employs DFT calculations to investigate whether the catalytic generation of O2 using ClO- follows the same mechanism previously identified with HSO5 - as the oxidant, or if it proceeds through an alternate pathway. To this end, we explored multiple pathways using ClO- as the oxidant. Interestingly, our findings confirm that in the case of ClO- as the oxidant, similar to what was observed with HSO5-, the Mn(IV)Mn (IV)-oxyl species indeed plays a crucial role in driving the catalytic evolution of O2 with the potential formation of the binuclear complexes Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH during the reaction. These complexes are reactive in producing O2, with activation free energies of 15.9 and 14.3 kcal mol-1, respectively. However, our calculations revealed that the Mn(IV)Mn(IV)-oxyl complex is significantly more reactive in producing O2 than Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH, with a lower free energy barrier of 8.1 kcal mol-1. Consequently, even though Mn(IV)Mn(IV)-oxyl is predicted to be present in much lower concentrations than Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH, it emerges as the species acting as the active catalyst for catalytic O2 generation. This study enhances our knowledge of high oxidation state (+3 and +4) manganese chemistry, highlighting its key role in catalysis and paving the way for more efficient Mnbased catalysts with broad applications. [ABSTRACT FROM AUTHOR] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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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| Header | DbId: egs DbLabel: Engineering Source An: 177140548 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Elucidating the catalytic mechanisms of O<subscript>2</subscript> generation by [Mn<subscript>2</subscript>(µ-O)<subscript>2</subscript>(terpy)<subscript>2</subscript>(OH<subscript>2</subscript>)<subscript>2</subscript>]<superscript>3+</superscript> using DFT calculations: a focus on ClO<superscript>-</superscript> as oxidant. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Ariafard%2C+Alireza%22">Ariafard, Alireza</searchLink><relatesTo>1</relatesTo><i> Alireza.Ariafard@anu.edu.au</i><br /><searchLink fieldCode="AR" term="%22Longhurst%2C+Matthew%22">Longhurst, Matthew</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Swiegers%2C+Gerhard+F%2E%22">Swiegers, Gerhard F.</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Stranger%2C+Robert%22">Stranger, Robert</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 5/7/2024, Vol. 53 Issue 17, p7580-7589. 10p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Oxidizing+agents%22">Oxidizing agents</searchLink><br /><searchLink fieldCode="DE" term="%22Activation+energy%22">Activation energy</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation+states%22">Oxidation states</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The experimentally reported Mn(IV)Mn(III) complex [Mn2(µ-O)2(terpy)2(OH2)2]3+ has been observed catalyzing O2 generation with oxidants like ClO- and HSO5-. Previous mechanistic studies primarily focused onO2 generation with HSO5-, concluding that Mn(IV)Mn(III) acts as a catalyst, generating a Mn(IV)Mn(IV)-oxyl species as a key intermediate responsible for O-O bond formation. This computational study employs DFT calculations to investigate whether the catalytic generation of O2 using ClO- follows the same mechanism previously identified with HSO5 - as the oxidant, or if it proceeds through an alternate pathway. To this end, we explored multiple pathways using ClO- as the oxidant. Interestingly, our findings confirm that in the case of ClO- as the oxidant, similar to what was observed with HSO5-, the Mn(IV)Mn (IV)-oxyl species indeed plays a crucial role in driving the catalytic evolution of O2 with the potential formation of the binuclear complexes Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH during the reaction. These complexes are reactive in producing O2, with activation free energies of 15.9 and 14.3 kcal mol-1, respectively. However, our calculations revealed that the Mn(IV)Mn(IV)-oxyl complex is significantly more reactive in producing O2 than Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH, with a lower free energy barrier of 8.1 kcal mol-1. Consequently, even though Mn(IV)Mn(IV)-oxyl is predicted to be present in much lower concentrations than Mn(IV)Mn(IV)-oxy and Mn(IV)Mn(IV)-OH, it emerges as the species acting as the active catalyst for catalytic O2 generation. This study enhances our knowledge of high oxidation state (+3 and +4) manganese chemistry, highlighting its key role in catalysis and paving the way for more efficient Mnbased catalysts with broad applications. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry 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: 10.1039/d4dt00734d Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 10 StartPage: 7580 Subjects: – SubjectFull: Oxidizing agents Type: general – SubjectFull: Activation energy Type: general – SubjectFull: Oxidation states Type: general Titles: – TitleFull: Elucidating the catalytic mechanisms of O2 generation by [Mn2(µ-O)2(terpy)2(OH2)2]3+ using DFT calculations: a focus on ClO- as oxidant. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Ariafard, Alireza – PersonEntity: Name: NameFull: Longhurst, Matthew – PersonEntity: Name: NameFull: Swiegers, Gerhard F. – PersonEntity: Name: NameFull: Stranger, Robert IsPartOfRelationships: – BibEntity: Dates: – D: 07 M: 05 Text: 5/7/2024 Type: published Y: 2024 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 53 – Type: issue Value: 17 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
| ResultId | 1 |
