Articles producció científica> Química Física i Inorgànica

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

  • Identification data

    Identifier: imarina:5129412
    Authors:
    Plessow, Philipp N.Carbo, Jorge J.Schaefer, AnsgarHofmann, Peter
    Abstract:
    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.
  • Others:

    Author, as appears in the article.: Plessow, Philipp N.; Carbo, Jorge J.; Schaefer, Ansgar; Hofmann, Peter;
    Department: Química Física i Inorgànica
    URV's Author/s: Carbó Martin, Jorge Juan
    Keywords: 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
    Abstract: 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.
    Thematic Areas: 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
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: j.carbo@urv.cat
    Author identifier: 0000-0002-3945-6721
    Record's date: 2024-09-07
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.organomet.5b00435
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Organometallics. 34 (15): 3764-3773
    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
    Article's DOI: 10.1021/acs.organomet.5b00435
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2015
    Publication Type: Journal Publications
  • Keywords:

    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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