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Ru‐Catalyzed Alkene Hydrophosphination: Correlating Substrate Scope with An Outer‐Sphere Mechanism.

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Title: Ru‐Catalyzed Alkene Hydrophosphination: Correlating Substrate Scope with An Outer‐Sphere Mechanism.
Authors: Yang, Jin1 (AUTHOR), Akar, Afsaneh1 (AUTHOR), Kellinghusen, Alexis M.1 (AUTHOR), Rosenberg, Lisa1 (AUTHOR) lisarose@uvic.ca
Source: ChemCatChem. 6/6/2025, Vol. 17 Issue 11, p1-10. 10p.
Subjects: Catalyst selectivity, Alkenes, Phosphine, Phosphines, Oligomerization
Abstract: A detailed examination of substrate scope is described for alkene hydrophosphination catalyzed by a series of Cp*Ru complexes. An outer‐sphere mechanism is proposed that involves nucleophilic addition of a Ru phosphido ligand to the alkene and subsequent proton transfer to the resulting phospha‐carbanion from Ru‐bound substrate phosphine. Selected kinetic studies and the observation of catalyst resting state complexes that inevitably contain both a reactive phosphido ligand and substrate phosphine suggest that the conjugate addition is turnover limiting. However, analysis of catalyst activities as a function of the alkene activating group, and observation of off‐cycle alkene oligomerization initiated by the phospha‐carbanion intermediate for some alkene and phosphine substrates point to a more complex situation. These results suggest that alkenes that are "too" activated or substrate phosphines that are not sufficiently P─H acidic cause the intramolecular proton transfer to become turnover‐limiting, with rates sensitive to the conjugate addition "pre‐equilibrium". This unusual compilation of experimental evidence for the impact of substrate variation on the activity and selectivity of a hydrophosphination catalyst provides insights for guiding future catalyst (re)design, including the challenge of providing a coordination environment that enhances phosphine P─H acidity to achieve a broader substrate phosphine scope. [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: Ru‐Catalyzed Alkene Hydrophosphination: Correlating Substrate Scope with An Outer‐Sphere Mechanism.
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  Data: <searchLink fieldCode="JN" term="%22ChemCatChem%22">ChemCatChem</searchLink>. 6/6/2025, Vol. 17 Issue 11, p1-10. 10p.
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  Data: <searchLink fieldCode="DE" term="%22Catalyst+selectivity%22">Catalyst selectivity</searchLink><br /><searchLink fieldCode="DE" term="%22Alkenes%22">Alkenes</searchLink><br /><searchLink fieldCode="DE" term="%22Phosphine%22">Phosphine</searchLink><br /><searchLink fieldCode="DE" term="%22Phosphines%22">Phosphines</searchLink><br /><searchLink fieldCode="DE" term="%22Oligomerization%22">Oligomerization</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: A detailed examination of substrate scope is described for alkene hydrophosphination catalyzed by a series of Cp*Ru complexes. An outer‐sphere mechanism is proposed that involves nucleophilic addition of a Ru phosphido ligand to the alkene and subsequent proton transfer to the resulting phospha‐carbanion from Ru‐bound substrate phosphine. Selected kinetic studies and the observation of catalyst resting state complexes that inevitably contain both a reactive phosphido ligand and substrate phosphine suggest that the conjugate addition is turnover limiting. However, analysis of catalyst activities as a function of the alkene activating group, and observation of off‐cycle alkene oligomerization initiated by the phospha‐carbanion intermediate for some alkene and phosphine substrates point to a more complex situation. These results suggest that alkenes that are "too" activated or substrate phosphines that are not sufficiently P─H acidic cause the intramolecular proton transfer to become turnover‐limiting, with rates sensitive to the conjugate addition "pre‐equilibrium". This unusual compilation of experimental evidence for the impact of substrate variation on the activity and selectivity of a hydrophosphination catalyst provides insights for guiding future catalyst (re)design, including the challenge of providing a coordination environment that enhances phosphine P─H acidity to achieve a broader substrate phosphine scope. [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.202500153
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      – Code: eng
        Text: English
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        PageCount: 10
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      – SubjectFull: Catalyst selectivity
        Type: general
      – SubjectFull: Alkenes
        Type: general
      – SubjectFull: Phosphine
        Type: general
      – SubjectFull: Phosphines
        Type: general
      – SubjectFull: Oligomerization
        Type: general
    Titles:
      – TitleFull: Ru‐Catalyzed Alkene Hydrophosphination: Correlating Substrate Scope with An Outer‐Sphere Mechanism.
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            NameFull: Akar, Afsaneh
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            NameFull: Kellinghusen, Alexis M.
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            NameFull: Rosenberg, Lisa
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            – D: 06
              M: 06
              Text: 6/6/2025
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              Y: 2025
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