Get access

Mechanism of Side Reactions in Alkane C[BOND]H Bond Functionalization by Diazo Compounds Catalyzed by Ag and Cu Homoscorpionate Complexes—A DFT Study

Authors

  • Dr. Ataualpa A. C. Braga,

    1. Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Catalonia (Spain), Fax: (+34) 977 920 231
    Search for more papers by this author
  • Dr. Ana Caballero,

    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007 Huelva (Spain)
    Search for more papers by this author
  • Dr. Juan Urbano,

    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007 Huelva (Spain)
    Search for more papers by this author
  • Dr. M. Mar Diaz-Requejo,

    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007 Huelva (Spain)
    Search for more papers by this author
  • Prof. Dr. Pedro J. Pérez,

    Corresponding author
    1. Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007 Huelva (Spain)
    • Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencia de los Materiales, Unidad Asociada al CSIC, Universidad de Huelva, Campus de El Carmen, 21007 Huelva (Spain)
    Search for more papers by this author
  • Prof. Dr. Feliu Maseras

    Corresponding author
    1. Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Catalonia (Spain), Fax: (+34) 977 920 231
    2. Departament de Química, Universitat Autônoma de Barcelona, 08193 Bellaterra, Catalonia (Spain)
    • Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Catalonia (Spain), Fax: (+34) 977 920 231
    Search for more papers by this author

Abstract

DFT computational methods were applied to the mechanistic study of the formation of fumarate and maleate derivatives in a solution containing alkane, TpBr3M [M=Cu, Ag; TpBr3=hydrotris(3,4,5-tribromopyrazolyl)borate] and methyl diazoacetate. These solutions are the experimentally reported conditions for carbene insertion into alkane C[BOND]H bonds, a procedure that usually competes with a nondesired reaction, producing fumarate and/or maleate derivatives. Several mechanisms are analyzed. The preferred mechanism proceeds through a direct reaction between a metallocarbene complex intermediate and a diazo molecule. The computational results explain all of the available experimental evidence and provide important information on the behavior of these systems.

Get access to the full text of this article

Ancillary