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