Articles producció científica> Química Física i Inorgànica

Two Copper-Carbenes from One Diazo Compound

  • Identification data

    Identifier: imarina:9182606
    Authors:
    Alvarez, MariaBesora, MariaMolina, FranciscoMaseras, FeliuBelderrain, Tomas R.Perez, Pedro J.
    Abstract:
    Many transition-metal complexes MLn decompose diazo compounds N-2=(CRR2)-R-1 generating metal-carbenes LnM=(CRR2)-R-1 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the (CRR2)-R-1 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the (CRR2)-R-1 ligand has undergone a modification from the initial diazo reagent. When Tp(Ms)Cu(THF) (Tp(Ms) = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N-2=C(H)(CONEt2)], the stable copper carbene Tp(Ms)Cu=C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as Tp(Ms)Cu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected Tp(Ms)Cu=C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.
  • Others:

    Author, as appears in the article.: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.;
    Department: Química Física i Inorgànica
    e-ISSN: 1520-5126
    URV's Author/s: Besora Bonet, Maria
    Keywords: Transition metals Synthesis (chemical) Simultaneous observation Reagent Organic synthesis Organic compounds Microkinetic models Metal complexes Metal complex Metal carbenes Ligands Ligand Kinetics Hydrogen bond Hydrogen Diazo compounds Dft calculation Density functional theory Decarbonylations Decarbonylation Copper compounds Copper Chemical modification Carbon monoxide Carbon Carbene insertion Carbene Calculation Article
    Abstract: Many transition-metal complexes MLn decompose diazo compounds N-2=(CRR2)-R-1 generating metal-carbenes LnM=(CRR2)-R-1 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the (CRR2)-R-1 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the (CRR2)-R-1 ligand has undergone a modification from the initial diazo reagent. When Tp(Ms)Cu(THF) (Tp(Ms) = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N-2=C(H)(CONEt2)], the stable copper carbene Tp(Ms)Cu=C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as Tp(Ms)Cu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected Tp(Ms)Cu=C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.
    Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0002-7863
    Author's mail: maria.besora@urv.cat
    Author identifier: 0000-0002-6656-5827
    Record's date: 2024-07-27
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/jacs.1c01483
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Journal Of The American Chemical Society. 143 (12): 4837-4843
    APA: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.; (2021). Two Copper-Carbenes from One Diazo Compound. Journal Of The American Chemical Society, 143(12), 4837-4843. DOI: 10.1021/jacs.1c01483
    Article's DOI: 10.1021/jacs.1c01483
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2021
    Publication Type: Journal Publications
  • Keywords:

    Biochemistry,Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Colloid and Surface Chemistry
    Transition metals
    Synthesis (chemical)
    Simultaneous observation
    Reagent
    Organic synthesis
    Organic compounds
    Microkinetic models
    Metal complexes
    Metal complex
    Metal carbenes
    Ligands
    Ligand
    Kinetics
    Hydrogen bond
    Hydrogen
    Diazo compounds
    Dft calculation
    Density functional theory
    Decarbonylations
    Decarbonylation
    Copper compounds
    Copper
    Chemical modification
    Carbon monoxide
    Carbon
    Carbene insertion
    Carbene
    Calculation
    Article
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Farmacia
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Colloid and surface chemistry
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Ciência de alimentos
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Biochemistry
    Astronomia / física
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