Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction

Journal article


Publication Details

Author(s): Gonell S, Caumes X, Orth N, Ivanovic-Burmazovic I, Reek JNH
Journal: Chemical Science
Publication year: 2019
Volume: 10
Journal issue: 5
Pages range: 1316-1321
ISSN: 2041-6520


Abstract


The application of large M
12
L
24
nanospheres allows the pre-concentration of catalysts to reach high local concentrations, facilitating reactions that proceed through dinuclear mechanisms. The mechanism of the copper(i)-catalyzed cyclization of 4-pentynoic acid has been elucidated by means of a detailed mechanistic study. The kinetics of the reaction show a higher order in copper, indicating the formation of a bis-Cu intermediate as the key rate determining step of the reaction. This intermediate was further identified during catalysis by CIS-HRMS analysis of the reaction mixture. Based on the mechanistic findings, an M
12
L
24
nanosphere was applied that can bind up to 12 copper catalysts by hydrogen bonding. This pre-organization of copper catalysts in the nanosphere results in a high local concentration of copper leading to higher reaction rates and turnover numbers as the dinuclear pathway is favored.


FAU Authors / FAU Editors

Ivanovic-Burmazovic, Ivana Prof. Dr.
Lehrstuhl für Bioanorganische Chemie
Orth, Nicole
Lehrstuhl für Bioanorganische Chemie


External institutions with authors

University of Amsterdam


How to cite

APA:
Gonell, S., Caumes, X., Orth, N., Ivanovic-Burmazovic, I., & Reek, J.N.H. (2019). Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction. Chemical Science, 10(5), 1316-1321. https://dx.doi.org/10.1039/c8sc03767a

MLA:
Gonell, Sergio, et al. "Self-assembled M12L24nanospheres as a reaction vessel to facilitate a dinuclear Cu(i) catalyzed cyclization reaction." Chemical Science 10.5 (2019): 1316-1321.

BibTeX: 

Last updated on 2019-07-05 at 07:23