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From the same journal

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

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Published copy (DOI)


  • Alexios Grigoropoulos
  • George F.S. Whitehead
  • Noémie Perret
  • Alexandros P. Katsoulidis
  • F. Mark Chadwick
  • Robert P. Davies
  • Anthony Haynes
  • Lee Brammer
  • Andrew S. Weller
  • Jianliang Xiao
  • Matthew J. Rosseinsky


Publication details

JournalChemical Science
DateAccepted/In press - 1 Dec 2015
DateE-pub ahead of print - 8 Dec 2015
DatePublished (current) - 1 Mar 2016
Issue number3
Number of pages14
Pages (from-to)2037-2050
Early online date8/12/15
Original languageEnglish


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 quasi-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 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.

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