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Selective Carbon–Carbon Bond Activation of Oxirane by a Bisphosphine Pt(0) Complex—A Theoretical Study

  • Datos identificativos

    Identificador: imarina:5129412
    Autores:
    Plessow, Philipp N.Carbo, Jorge J.Schaefer, AnsgarHofmann, Peter
    Resumen:
    Platinum(0) complexes with the chelate ligand bis(di-tert-butylphosphino)methane, tBu2P-CH2-PtBu2 (dtbpm), generated in solution from appropriate precursors, are the only known transition metal species that selectively activate epoxides (oxiranes) by inserting the Pt fragment into their carbon¿carbon bond. The mechanism of this unprecedented reaction is studied theoretically using the random phase approximation. We find that the reaction is kinetically controlled and is caused by the formation of a monocoordinate (dtbpm-κ1P)Pt(0) fragment rather than a (dtbpm-κ2P)Pt(0) chelate complex. Insertion into epoxide C¿C bonds occurs without energy barrier. Conceivable competing reactions, oxirane C¿O and C¿H activation, both proceed via formation of a σ-complex, followed by small but significant barriers for insertion steps. A reversible formation of the σ-complexes would perfectly explain the observed reactivity. For an irreversible formation, we find that intramolecular rearrangement of these σ-complexes toward C¿C activation products is faster than both C¿O and C¿H activation. In principle, the same reactivity should be expected for other monocoordinated platinum(0) phosphine complexes. However, only the specific properties of dtbpm cause the subsequent, rapid, and irreversible closing of the chelate ligand yielding stable, square-planar Pt(II) C¿C activation products.
  • Otros:

    Autor según el artículo: Plessow, Philipp N.; Carbo, Jorge J.; Schaefer, Ansgar; Hofmann, Peter;
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Carbó Martin, Jorge Juan
    Palabras clave: Zeta-valence quality Transition-state method Substituted cyclopropanes Regular 2-component hamiltonians Reductive elimination-reactions Palladium(ii) complexes Hydrogen-bonds Electronic-structure Copper-catalyzed cyclopropanation C-h bonds
    Resumen: Platinum(0) complexes with the chelate ligand bis(di-tert-butylphosphino)methane, tBu2P-CH2-PtBu2 (dtbpm), generated in solution from appropriate precursors, are the only known transition metal species that selectively activate epoxides (oxiranes) by inserting the Pt fragment into their carbon¿carbon bond. The mechanism of this unprecedented reaction is studied theoretically using the random phase approximation. We find that the reaction is kinetically controlled and is caused by the formation of a monocoordinate (dtbpm-κ1P)Pt(0) fragment rather than a (dtbpm-κ2P)Pt(0) chelate complex. Insertion into epoxide C¿C bonds occurs without energy barrier. Conceivable competing reactions, oxirane C¿O and C¿H activation, both proceed via formation of a σ-complex, followed by small but significant barriers for insertion steps. A reversible formation of the σ-complexes would perfectly explain the observed reactivity. For an irreversible formation, we find that intramolecular rearrangement of these σ-complexes toward C¿C activation products is faster than both C¿O and C¿H activation. In principle, the same reactivity should be expected for other monocoordinated platinum(0) phosphine complexes. However, only the specific properties of dtbpm cause the subsequent, rapid, and irreversible closing of the chelate ligand yielding stable, square-planar Pt(II) C¿C activation products.
    Áreas temáticas: Química Physical and theoretical chemistry Organic chemistry Materiais Inorganic chemistry Engenharias ii Ciências biológicas ii Ciências agrárias i Chemistry, organic Chemistry, inorganic & nuclear Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: j.carbo@urv.cat
    Identificador del autor: 0000-0002-3945-6721
    Fecha de alta del registro: 2024-09-07
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.organomet.5b00435
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Organometallics. 34 (15): 3764-3773
    Referencia de l'ítem segons les normes APA: Plessow, Philipp N.; Carbo, Jorge J.; Schaefer, Ansgar; Hofmann, Peter; (2015). Selective Carbon–Carbon Bond Activation of Oxirane by a Bisphosphine Pt(0) Complex—A Theoretical Study. Organometallics, 34(15), 3764-3773. DOI: 10.1021/acs.organomet.5b00435
    DOI del artículo: 10.1021/acs.organomet.5b00435
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2015
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry, Inorganic & Nuclear,Chemistry, Organic,Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry
    Zeta-valence quality
    Transition-state method
    Substituted cyclopropanes
    Regular 2-component hamiltonians
    Reductive elimination-reactions
    Palladium(ii) complexes
    Hydrogen-bonds
    Electronic-structure
    Copper-catalyzed cyclopropanation
    C-h bonds
    Química
    Physical and theoretical chemistry
    Organic chemistry
    Materiais
    Inorganic chemistry
    Engenharias ii
    Ciências biológicas ii
    Ciências agrárias i
    Chemistry, organic
    Chemistry, inorganic & nuclear
    Astronomia / física
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