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

DOI: 10.1039/C5SC03494A DOI Help

Authors: Alexios Grigoropoulos (University of Liverpool) , George Whitehead (University of Liverpool) , Noemie Perret (University of Liverpool) , Alexandros Katsoulidis (University of Liverpool) , Mark Chadwick (University of Oxford) , Robert Davies (Imperial College London) , Anthony Haynes (University of Sheffield) , Lee Brammer (University of Sheffield) , Andrew Weller (University of Liverpool) , Jianliang Xiao (University of Liverpool) , Matthew Rosseinsky (University of Liverpool)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science

State: Published (Approved)
Published: December 2015

Open Access Open Access

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)2(L)]+ ([Fp-L]+, Cp = η5-C5H5, L = weakly bound solvent) inside the pores of the anionic [Et4N]3[In3(BTC)4] MOF (H3BTC = benzenetricarboxylic acid) via a direct one-step cation exchange process. To conclusively validate this methodology, initially [Cp2Co]+ 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 isosteric [Fp-L]+ was encapsulated inside the pores via partial cation exchange to form [(Fp-L)0.6(Et4N)2.4][In3(BTC)4]. The latter was rigorously characterized and benchmarked as a heterogeneous catalyst in a simple Diels-Alder reaction, thus verifying the cationic organometallic molecular catalyst’s integrity and reactivity after cation exchange. These results provide a platform for the development of heterogeneous catalysts with chemically and spatially well-defined catalytic sites by one-step cation exchange into MOFs.

Subject Areas: Chemistry, Materials

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 22/12/2015 13:03


Discipline Tags:

Physical Chemistry Catalysis Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)