Projects per year
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.
Original language | English |
---|---|
Pages (from-to) | 17646-17656 |
Number of pages | 11 |
Journal | Chemistry - A European Journal |
Volume | 22 |
Issue number | 49 |
Early online date | 27 Oct 2016 |
DOIs | |
Publication status | Published - 5 Dec 2016 |
Keywords
- cooperative effects
- guanidines
- homogeneous catalysis
- magnesiates
- s-block metals
- sodium magnesiate
- hydrophosphination
- carbodiimides
- guanylation reactions
Fingerprint
Dive into the research topics of 'Structural and mechanistic insights into s-block bimetallic catalysis: sodium magnesiate-catalyzed guanylation of amines'. Together they form a unique fingerprint.Projects
- 1 Finished
-
MIXMETAPPS: Tailoring Mixed-Metal Chemistry For Frontier Synthetic And Catalytic Applications (ERC Starting Grant)
Hevia, E.
European Commission - FP7 - European Research Council
1/10/11 → 31/03/17
Project: Research