Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment. Issue 17 (22nd March 2018)

• Record Type: Journal Article
• Authors: Grigoropoulos, Alexios; McKay, Alasdair I.; Katsoulidis, Alexandros P.; Davies, Robert P.; Haynes, Anthony; Brammer, Lee; Xiao, Jianliang; Weller, Andrew S.; Rosseinsky, Matthew J.
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 17(2018)
• Page Start: 4532
• Page End: 4537
• Publication Date: 2018-03-22
• Subjects: allylic alcohols -- Crabtree's catalyst -- encapsulation -- hydrogenation -- metal–organic frameworks; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201710091
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL‐101(Cr) metal–organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non‐functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well‐defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways. Abstract : Better in than out : Encapsulation of Crabtree's catalyst inside the sulfonated analogue of MIL‐101(Cr) by cation exchange significantly increases activity and selectivity to hydrogenation of olefinic alcohols with the MOF chemical microenvironment directing the substrate along one out of two competing reaction pathways.