Articles producció científica> Química Física i Inorgànica

Quantitative Structure-Activity Relationships for the nucleophilicity of trivalent boron compounds

  • Identification data

    Identifier: imarina:3672242
    Authors:
    García-López D, Cid J, Marqués R, Fernández E, Carbó JJ
    Abstract:
    We describe herein the development of quantitative structure-activity relationships (QSAR) for the nucleophilicity of trivalent boron compounds covering boryl fragments bonded to alkali and alkaline-earth metals, to transition metals, and to sp3 boron units in diboron reagents. We used the charge of the boryl fragment (q[B]) and the boron p/s population ratio (p/s) to describe the electronic structures of boryl moieties, whereas the distance-weighted volume (Vw ) descriptor was used to evaluate the steric effects. The three-term easy-to-interpret QSAR model showed statistical significance and predictive ability (r2 =0.88, q2 =0.83). The use of chemically meaningful descriptors has allowed identification of the factors governing the boron nucleophilicity and indicates that the most efficient nucleophiles are those with enhanced the polarization of the B-X bond towards the boron atom and reduced steric bulk. A detailed analysis of the potential energy surfaces of different types of boron substituents has provided insight into the mechanism and established an order of nucleophilicity for boron in B-X: X=Li>Cu>B(sp3 )>Pd. Finally, we used the QSAR model to make a priori predictions of experimentally untested compounds.
  • Others:

    Author, as appears in the article.: García-López D, Cid J, Marqués R, Fernández E, Carbó JJ
    Department: Química Física i Inorgànica
    e-ISSN: 1521-3765
    URV's Author/s: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena
    Keywords: Affordable and clean energy
    Abstract: We describe herein the development of quantitative structure-activity relationships (QSAR) for the nucleophilicity of trivalent boron compounds covering boryl fragments bonded to alkali and alkaline-earth metals, to transition metals, and to sp3 boron units in diboron reagents. We used the charge of the boryl fragment (q[B]) and the boron p/s population ratio (p/s) to describe the electronic structures of boryl moieties, whereas the distance-weighted volume (Vw ) descriptor was used to evaluate the steric effects. The three-term easy-to-interpret QSAR model showed statistical significance and predictive ability (r2 =0.88, q2 =0.83). The use of chemically meaningful descriptors has allowed identification of the factors governing the boron nucleophilicity and indicates that the most efficient nucleophiles are those with enhanced the polarization of the B-X bond towards the boron atom and reduced steric bulk. A detailed analysis of the potential energy surfaces of different types of boron substituents has provided insight into the mechanism and established an order of nucleophilicity for boron in B-X: X=Li>Cu>B(sp3 )>Pd. Finally, we used the QSAR model to make a priori predictions of experimentally untested compounds.
    Thematic Areas: Química Organic chemistry Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias iii Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biotecnología Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: j.carbo@urv.cat mariaelena.fernandez@urv.cat
    Author identifier: 0000-0002-3945-6721 0000-0001-9025-1791
    Record's date: 2024-11-16
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/chem.201605798
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Chemistry-A European Journal. 23 (21): 5066-5075
    APA: García-López D, Cid J, Marqués R, Fernández E, Carbó JJ (2017). Quantitative Structure-Activity Relationships for the nucleophilicity of trivalent boron compounds. Chemistry-A European Journal, 23(21), 5066-5075. DOI: 10.1002/chem.201605798
    Article's DOI: 10.1002/chem.201605798
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2017
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Organic Chemistry
    Affordable and clean energy
    Química
    Organic chemistry
    Medicina i
    Materiais
    Interdisciplinar
    General medicine
    General chemistry
    Farmacia
    Engenharias iii
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Biotecnología
    Biodiversidade
    Astronomia / física
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