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Mechanistic elucidation of O2 production from tBuOOH in water using the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+: a DFT study.

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Title: Mechanistic elucidation of O2 production from tBuOOH in water using the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+: a DFT study.
Authors: Ariafard, Alireza1 Alireza.Ariafard@anu.edu.au, Longhurst, Matthew2, Swiegers, Gerhard F.2, Stranger, Robert1 rob.stranger@anu.edu.au
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 9/7/2024, Vol. 53 Issue 33, p14089-14097. 9p.
Subjects: Water use, Catalysts, Density functional theory, Oxidation states, Renewable energy sources
Abstract: This study employs density functional theory at the SMD/B3LYP-D3/6-311+G(2d,p),def2-TZVPP//SMD/B3LYP-D3/6-31G(d),SDD level of theory to explore the mechanistic details of O2 generation from tBuOOH, using H218O as the solvent, in the presence of the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+. Since this chemistry was reported to occur through the reaction of Mn(III)(μ-O)Mn(IV)–O˙ with water, we first revaluated this proposal and found that it occurs with an activation barrier greater than 36 kcal mol−1, ruling out the functioning of such a dimer as the active catalyst. Experimental evidence has shown that the oxidation of [Mn2(mcbpen)2(H2O)2]2+ by tBuOOH in H218O produces the Mn(IV) species [Mn(18O)(mcbpen)]+. Our investigations revealed a plausible mechanism for this observation in which [Mn (18O)(mcbpen)]+ acts as the active catalyst, generating the tert-butyl peroxyl radical (tBuOO˙) through its reaction with tBuOOH. In this proposed mechanism, the O–O bond is formed through the interaction of tBuOO˙ with another [Mn(18O)(mcbpen)]+, finally leading to the formation of the 16O＝18O product. Our findings underscore the pivotal role of [Mn(18O)(mcbpen)]+ in both generating the active species tBuOO˙ and consuming it to produce 16O＝18O. With activation barriers as low as about 9 kcal mol−1, these elementary steps highlight the feasibility of our proposed mechanism. Moreover, this mechanism elucidates why, experimentally, one of the oxygen atoms in the released O2 comes from water, while the other originates from tBuOOH. This research broadens our understanding of high oxidation state manganese chemistry, setting the stage for the development of more efficient Mn-based catalysts, aimed at improving processes in both renewable energy and synthetic chemistry. [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.)
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  Data: Mechanistic elucidation of O<subscript>2</subscript> production from <superscript>t</superscript>BuOOH in water using the Mn(II) catalyst [Mn<subscript>2</subscript>(mcbpen)<subscript>2</subscript>(H<subscript>2</subscript>O)<subscript>2</subscript>]<superscript>2+</superscript>: a DFT study.
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  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><i> rob.stranger@anu.edu.au</i>
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 9/7/2024, Vol. 53 Issue 33, p14089-14097. 9p.
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  Data: <searchLink fieldCode="DE" term="%22Water+use%22">Water use</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation+states%22">Oxidation states</searchLink><br /><searchLink fieldCode="DE" term="%22Renewable+energy+sources%22">Renewable energy sources</searchLink>
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  Label: Abstract
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  Data: This study employs density functional theory at the SMD/B3LYP-D3/6-311+G(2d,p),def2-TZVPP//SMD/B3LYP-D3/6-31G(d),SDD level of theory to explore the mechanistic details of O2 generation from tBuOOH, using H218O as the solvent, in the presence of the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+. Since this chemistry was reported to occur through the reaction of Mn(III)(μ-O)Mn(IV)–O˙ with water, we first revaluated this proposal and found that it occurs with an activation barrier greater than 36 kcal mol−1, ruling out the functioning of such a dimer as the active catalyst. Experimental evidence has shown that the oxidation of [Mn2(mcbpen)2(H2O)2]2+ by tBuOOH in H218O produces the Mn(IV) species [Mn(18O)(mcbpen)]+. Our investigations revealed a plausible mechanism for this observation in which [Mn (18O)(mcbpen)]+ acts as the active catalyst, generating the tert-butyl peroxyl radical (tBuOO˙) through its reaction with tBuOOH. In this proposed mechanism, the O–O bond is formed through the interaction of tBuOO˙ with another [Mn(18O)(mcbpen)]+, finally leading to the formation of the 16O＝18O product. Our findings underscore the pivotal role of [Mn(18O)(mcbpen)]+ in both generating the active species tBuOO˙ and consuming it to produce 16O＝18O. With activation barriers as low as about 9 kcal mol−1, these elementary steps highlight the feasibility of our proposed mechanism. Moreover, this mechanism elucidates why, experimentally, one of the oxygen atoms in the released O2 comes from water, while the other originates from tBuOOH. This research broadens our understanding of high oxidation state manganese chemistry, setting the stage for the development of more efficient Mn-based catalysts, aimed at improving processes in both renewable energy and synthetic chemistry. [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:
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      – Type: doi
        Value: 10.1039/d4dt01700e
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 9
        StartPage: 14089
    Subjects:
      – SubjectFull: Water use
        Type: general
      – SubjectFull: Catalysts
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Oxidation states
        Type: general
      – SubjectFull: Renewable energy sources
        Type: general
    Titles:
      – TitleFull: Mechanistic elucidation of O2 production from tBuOOH in water using the Mn(II) catalyst [Mn2(mcbpen)2(H2O)2]2+: a DFT study.
        Type: main
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      – PersonEntity:
          Name:
            NameFull: Ariafard, Alireza
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            NameFull: Longhurst, Matthew
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            NameFull: Swiegers, Gerhard F.
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            NameFull: Stranger, Robert
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          Dates:
            – D: 07
              M: 09
              Text: 9/7/2024
              Type: published
              Y: 2024
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              Value: 53
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              Value: 33
          Titles:
            – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry
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