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Large Isotope Effects in Organometallic Chemistry

Truong, Phan T. ; Miller, Sophia G. ; McLaughlin Sta. Maria, Emily J. ; Bowring, Miriam A.

Chemistry : a European journal, 2021-10, Vol.27 (60), p.14800-14815 [Periódico revisado por pares]

Weinheim: Wiley Subscription Services, Inc

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  • Título:
    Large Isotope Effects in Organometallic Chemistry
  • Autor: Truong, Phan T. ; Miller, Sophia G. ; McLaughlin Sta. Maria, Emily J. ; Bowring, Miriam A.
  • Assuntos: Chemistry ; Coordination compounds ; C−H activation ; Deuterium ; Intermediates ; Isotope effect ; isotope effects ; kinetics ; Organometallic complexes ; Organometallic compounds ; Protonation ; Protons ; Rate constants ; Reaction mechanisms ; Transition metals
  • É parte de: Chemistry : a European journal, 2021-10, Vol.27 (60), p.14800-14815
  • Notas: ObjectType-Article-2
    SourceType-Scholarly Journals-1
    ObjectType-Feature-3
    ObjectType-Review-1
  • Descrição: The kinetic isotope effect (KIE) is key to understanding reaction mechanisms in many areas of chemistry and chemical biology, including organometallic chemistry. This ratio of rate constants, kH/kD, typically falls between 1–7. However, KIEs up to 105 have been reported, and can even be so large that reactivity with deuterium is unobserved. We collect here examples of large KIEs across organometallic chemistry, in catalytic and stoichiometric reactions, along with their mechanistic interpretations. Large KIEs occur in proton transfer reactions such as protonation of organometallic complexes and clusters, protonolysis of metal–carbon bonds, and dihydrogen reactivity. C−H activation reactions with large KIEs occur with late and early transition metals, photogenerated intermediates, and ion by metal‐oxo complexes. We categorize the mechanistic interpretations of large KIEs into the following three types: (a) proton tunneling, (b) compound effects from multiple steps, and (c) semi‐classical effects on a single step. This comprehensive collection of large KIEs in organometallics provides context for future mechanistic interpretation. Kinetic isotope effects (KIEs, kH/kD) above the typical limit of 7 are reviewed, for organometallic reaction types from protonation of clusters to catalytic C−H activation. The KIEs are as large as 105, or even so large that reactivity is unobserved for deuterium. Large KIEs in organometallics have been explained by a combination of (a) proton tunneling, (b) compound effects from multiple steps, and (c) semi‐classical effects on a single step.
  • Editor: Weinheim: Wiley Subscription Services, Inc
  • Idioma: Inglês
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  • Realização: ABCD-USP USP   Logos de Redes Sociais: Freepik

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