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Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators.

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Title: Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators.
Authors: Valerie J. Scott1, Jay A. Labinger1, John E. Bercaw1
Source: Organometallics. Aug2011, Vol. 30 Issue 16, p4374-4378. 5p.
Subjects: Chemical kinetics, Isotopes, Proton transfer reactions, Transition metal complexes, Quantum chemistry, Quantum tunneling, Reaction mechanisms (Chemistry), Statistical correlation
Abstract: Earlier work on protonolyses of several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal–methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension of these measurements to a wider set of complexes, we find no support for the proposed correlation. [ABSTRACT FROM AUTHOR]
Copyright of Organometallics 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
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PubType: Academic Journal
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  Data: Earlier work on protonolyses of several palladium and platinum methyl complexes (with release of methane) had suggested the possibility that observation of an unusually large kinetic isotope effect, consistent with significant contributions from quantum mechanical tunneling, might be diagnostic of a mechanism involving direct protonation of the metal–methyl bond, as opposed to one proceeding via a metal hydride intermediate. By extension of these measurements to a wider set of complexes, we find no support for the proposed correlation. [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Organometallics 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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        Value: 10.1021/om200432b
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      – Code: eng
        Text: English
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      – SubjectFull: Chemical kinetics
        Type: general
      – SubjectFull: Isotopes
        Type: general
      – SubjectFull: Proton transfer reactions
        Type: general
      – SubjectFull: Transition metal complexes
        Type: general
      – SubjectFull: Quantum chemistry
        Type: general
      – SubjectFull: Quantum tunneling
        Type: general
      – SubjectFull: Reaction mechanisms (Chemistry)
        Type: general
      – SubjectFull: Statistical correlation
        Type: general
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      – TitleFull: Large Kinetic Isotope Effects for the Protonolysis of Metal–Methyl Complexes Are Not Reliable Mechanistic Indicators.
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              Text: Aug2011
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              Y: 2011
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