title: Structural and Mechanistic Insights into s-Block Bimetallic Catalysis: Sodium Magnesiate-Catalyzed Guanylation of Amines.
abstract: To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with carbodiimides. First examples of hydrophosphination of carbodiimides by using a Mg catalyst are also described. The catalytic ability of the mixed-metal system is much greater than that of its homometallic components [NaCH2SiMe3] and [Mg(CH2SiMe3)2]. Stoichiometric studies suggest that magnesiate amido and guanidinate complexes are intermediates in these catalytic routes. Reactivity and kinetic studies imply that these guanylation reactions occur via (tris)amide intermediates that react with carbodiiimides in insertion steps. The rate law for the guanylation of N,N'-diisopropylcarbodiimide with 4-tert-butylaniline catalyzed by 1 is first order with respect to [amine], [carbodiimide], and [catalyst], and the reaction shows a large kinetic isotopic effect, which is consistent with an amine-assisted rate-determining carbodiimide insertion transition state. Studies to assess the effect of sodium in these transformations denote a secondary role with little involvement in the catalytic cycle.
authors: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors: Marco
authors: M
authors: De Tullio
authors: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors: Alberto
authors: A
authors: Hernán-Gómez
authors: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors: Zoe
authors: Z
authors: Livingstone
authors: School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK.
authors: William
authors: W
authors: Clegg
authors: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors: Alan R
authors: AR
authors: Kennedy
authors: School of Chemistry, Newcastle University, Newcastle upon Tyne, NE1 7RU, UK.
authors: Ross W
authors: RW
authors: Harrington
authors: Centro de Innovación en Química Avanzada (ORFEO-CINQA) Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha Campus Universitario, 13071, Ciudad Real, Spain.
authors: Antonio
authors: A
authors: Antiñolo
authors: Centro de Innovación en Química Avanzada (ORFEO-CINQA) Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha Campus Universitario, 13071, Ciudad Real, Spain.
authors: Antonio
authors: A
authors: Martínez
authors: Centro de Innovación en Química Avanzada (ORFEO-CINQA) Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha Campus Universitario, 13071, Ciudad Real, Spain.
authors: Fernando
authors: F
authors: Carrillo-Hermosilla
authors: WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL, UK.
authors: Eva
authors: http://orcid.org/0000-0002-3998-7506
authors: E
authors: Hevia
keywords: cooperative effects; guanidines; homogeneous catalysis; magnesiates; s-block metals