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
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  • 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)
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  • 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)
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  • 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)
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  • 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)
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  • 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
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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.

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