Toggle Main Menu Toggle Search

Open Access padlockePrints

Structural and Mechanistic Insights into s-Block Bimetallic Catalysis: Sodium Magnesiate-Catalyzed Guanylation of Amines

Lookup NU author(s): Emeritus Professor Bill CleggORCiD, Dr Ross Harrington


Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


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.

Publication metadata

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


DOI: 10.1002/chem.201602906


Altmetrics provided by Altmetric


Funder referenceFunder name
European Research Council
University of Strathclyde
CTQ2014-51912-REDCSpanish Ministerio de Economia y Competitividad (MINECO)
PEII-2014-041-PJunta de Comunidades de Castilla-La Mancha