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Effect of Unique NNS Ligand in Manganese‐Catalyzed Transfer Hydrogenation Reaction—A DFT Mechanistic Study.

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Title: Effect of Unique NNS Ligand in Manganese‐Catalyzed Transfer Hydrogenation Reaction—A DFT Mechanistic Study.
Authors: Guo, Cai‐Hong1,2 (AUTHOR) sxgch2006@163.com, Zhou, Daimei1 (AUTHOR), Jiao, Haijun3 (AUTHOR) haijun.jiao@catalysis.de
Source: ChemCatChem. 1/28/2026, Vol. 18 Issue 2, p1-11. 11p.
Subjects: Transfer hydrogenation, Density functional theory, Isopropyl alcohol, Manganese catalysts, Mechanism (Philosophy), Metal complexes, Acetophenone, Reaction mechanisms (Chemistry)
Abstract: The transfer hydrogenation between isopropanol and acetophenone catalyzed by phosphine‐free cationic [NNS‐Mn(CO)3]+complexes bearing sulfur‐arm ligand has been computed. Since base treatment can have two active amido complexes, bidentate NN‐Mn(CO)3 with sulfur‐arm ligand as spectator or tridentate NNS‐Mn(CO)2 involving the sulfur‐arm have been considered. The bidentate complexes are more active in isopropanol dehydrogenation, and the tridentate complexes are more active in acetophenone hydrogenation; however, both complexes have rather low apparent barriers, rationalizing the reaction conditions at room temperature and ambient pressure. It is noted that isopropanol dehydrogenation prefers an outer‐sphere mechanism and represents the rate‐determining step. On the contrary to isopropanol as a hydrogen source, activation of H2 has a much higher barrier, explaining the rather lower activity under harsh conditions at high temperature and high pressure. [ABSTRACT FROM AUTHOR]
Copyright of ChemCatChem is the property of Wiley-Blackwell 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: Effect of Unique NNS Ligand in Manganese‐Catalyzed Transfer Hydrogenation Reaction—A DFT Mechanistic Study.
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  Data: <searchLink fieldCode="AR" term="%22Guo%2C+Cai‐Hong%22">Guo, Cai‐Hong</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<i> sxgch2006@163.com</i><br /><searchLink fieldCode="AR" term="%22Zhou%2C+Daimei%22">Zhou, Daimei</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Jiao%2C+Haijun%22">Jiao, Haijun</searchLink><relatesTo>3</relatesTo> (AUTHOR)<i> haijun.jiao@catalysis.de</i>
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  Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. 1/28/2026, Vol. 18 Issue 2, p1-11. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Transfer+hydrogenation%22">Transfer hydrogenation</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Isopropyl+alcohol%22">Isopropyl alcohol</searchLink><br /><searchLink fieldCode="DE" term="%22Manganese+catalysts%22">Manganese catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Mechanism+%28Philosophy%29%22">Mechanism (Philosophy)</searchLink><br /><searchLink fieldCode="DE" term="%22Metal+complexes%22">Metal complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Acetophenone%22">Acetophenone</searchLink><br /><searchLink fieldCode="DE" term="%22Reaction+mechanisms+%28Chemistry%29%22">Reaction mechanisms (Chemistry)</searchLink>
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  Label: Abstract
  Group: Ab
  Data: The transfer hydrogenation between isopropanol and acetophenone catalyzed by phosphine‐free cationic [NNS‐Mn(CO)3]+complexes bearing sulfur‐arm ligand has been computed. Since base treatment can have two active amido complexes, bidentate NN‐Mn(CO)3 with sulfur‐arm ligand as spectator or tridentate NNS‐Mn(CO)2 involving the sulfur‐arm have been considered. The bidentate complexes are more active in isopropanol dehydrogenation, and the tridentate complexes are more active in acetophenone hydrogenation; however, both complexes have rather low apparent barriers, rationalizing the reaction conditions at room temperature and ambient pressure. It is noted that isopropanol dehydrogenation prefers an outer‐sphere mechanism and represents the rate‐determining step. On the contrary to isopropanol as a hydrogen source, activation of H2 has a much higher barrier, explaining the rather lower activity under harsh conditions at high temperature and high pressure. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of ChemCatChem is the property of Wiley-Blackwell 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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      – Type: doi
        Value: 10.1002/cctc.202501586
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 11
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    Subjects:
      – SubjectFull: Transfer hydrogenation
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Isopropyl alcohol
        Type: general
      – SubjectFull: Manganese catalysts
        Type: general
      – SubjectFull: Mechanism (Philosophy)
        Type: general
      – SubjectFull: Metal complexes
        Type: general
      – SubjectFull: Acetophenone
        Type: general
      – SubjectFull: Reaction mechanisms (Chemistry)
        Type: general
    Titles:
      – TitleFull: Effect of Unique NNS Ligand in Manganese‐Catalyzed Transfer Hydrogenation Reaction—A DFT Mechanistic Study.
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            NameFull: Guo, Cai‐Hong
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            – D: 28
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              Text: 1/28/2026
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              Y: 2026
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