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Lookup NU author(s): Professor William Clegg, Dr Ross Harrington
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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.
Author(s): De Tullio M, Hernan-Gomez A, Livingstone Z, Clegg W, Kennedy AR, Harrington RW, Antinolo A, Martinez A, Carrillo-Hermosilla F, Hevia E
Publication type: Article
Publication status: Published
Journal: Chemistry: A European Journal
Year: 2016
Volume: 22
Issue: 49
Pages: 17646-17656
Print publication date: 05/12/2016
Online publication date: 27/10/2016
Acceptance date: 02/04/2016
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: Wiley - V C H Verlag GmbH & Co. KGaA
URL: http://dx.doi.org/10.1002/chem.201602906
DOI: 10.1002/chem.201602906
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