Encapsulation of an organometallic cationic catalyst by direct exchange into an anionic MOF



Grigoropoulos, Alexios ORCID: 0000-0002-3108-7052, Whitehead, George FS, Perret, Noemie, Katsoulidis, Alexandros P ORCID: 0000-0003-0860-7440, Chadwick, F Mark, Davies, Robert P, Haynes, Anthony, Brammer, Lee, Weller, Andrew S, Xiao, Jianliang ORCID: 0000-0003-2010-247X
et al (show 1 more authors) (2016) Encapsulation of an organometallic cationic catalyst by direct exchange into an anionic MOF. CHEMICAL SCIENCE, 7 (3). pp. 2037-2050.

[thumbnail of Grigoropoulos_Text_Revision1.pdf] Text
Grigoropoulos_Text_Revision1.pdf - Author Accepted Manuscript

Download (1MB)

Abstract

Metal-Organic Frameworks (MOFs) are porous crystalline materials that have emerged as promising hosts for the heterogenization of homogeneous organometallic catalysts, forming hybrid materials which combine the benefits of both classes of catalysts. Herein, we report the encapsulation of the organometallic cationic Lewis acidic catalyst [CpFe(CO)<sub>2</sub>(L)]<sup>+</sup> ([Fp-L]<sup>+</sup>, Cp = η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>, L = weakly bound solvent) inside the pores of the anionic [Et<sub>4</sub>N]<sub>3</sub>[In<sub>3</sub>(BTC)<sub>4</sub>] MOF (H<sub>3</sub>BTC = benzenetricarboxylic acid) <i>via</i> a direct one-step cation exchange process. To conclusively validate this methodology, initially [Cp<sub>2</sub>Co]<sup>+</sup> was used as an inert spatial probe to (i) test the stability of the selected host; (ii) monitor the stoichiometry of the cation exchange process and (iii) assess pore dimensions, spatial location of the cationic species and guest-accessible space by single crystal X-ray crystallography. Subsequently, the quasi-isosteric [Fp-L]<sup>+</sup> was encapsulated inside the pores <i>via</i> partial cation exchange to form [(Fp-L)<sub>0.6</sub>(Et<sub>4</sub>N)<sub>2.4</sub>][In<sub>3</sub>(BTC)<sub>4</sub>]. The latter was rigorously characterized and benchmarked as a heterogeneous catalyst in a simple Diels-Alder reaction, thus verifying the integrity and reactivity of the encapsulated molecular catalyst. These results provide a platform for the development of heterogeneous catalysts with chemically and spatially well-defined catalytic sites by direct exchange of cationic catalysts into anionic MOFs.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 05 Jul 2016 08:36
Last Modified: 15 Nov 2023 14:31
DOI: 10.1039/c5sc03494a
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3002087