Heterogenisation of a carbonylation catalyst on dispersible microporous polymer nanoparticles

Abstract

The methanol carbonylation catalyst, cis-[Rh(CO)2I2]–, has been heterogenised within a dispersible microporous polymer support bearing cationic functionality. The microporous polymer has a core-shell structure in which the porous and insoluble...

Ionic encapsulation of a methanol carbonylation catalyst in a microporous metal–organic framework

“…The carbonylation of MeOH/MeI catalysed by 3 was followed by in situ high-pressure IR spectroscopy, using a cylindrical internal reflectance (CIR) cell (S2.11, ESI†) as described previously. 11 During the reaction (at 120 °C, 10 bar CO in CHCl 3 ), growth of an absorption at 1741 cm −1 was observed (Fig. 3b and Fig S18, ESI†) which corresponds to the ν (CO) absorption of methyl acetate.…”

“…Using a strategy analogous to that employed previously to generate polymer-supported [Rh(CO) 2 I 2 ] − , 10,11 a sample of 2 was treated with the iodide bridged rhodium dimer [Rh(CO) 2 I] 2 , which reacts with the I − counter-ions in 2 (Scheme 2). The presence of a Rh( i ) complex cis -[Rh(CO) 2 I 2 ] − in the product 3 was confirmed by the presence of two ν (CO) absorptions at 2060 and 1986 cm −1 in the IR spectrum (Fig.…”

“…By comparison, a TOF of ∼20 h −1 was found in our recent study using a dispersible microporous polymer support. 11 The slower rate for the MOF-supported catalyst may indicate greater diffusion limitations for the MOF. PXRD of the recovered material following catalysis indicates crystallinity of the MOF is maintained (Fig.…”

“…8 This ionic attachment approach was later adopted in the Aceticat process developed by Chiyoda/UOP, which attains rates comparable with the homogeneous system but requires lower water concentrations and can employ a higher catalyst loading due to the removal of solubility constraints. 9 Mechanistic studies on related polymer-supported systems in our labs in Sheffield, 10 including a recent study using dispersible microporous nanoparticles, 11 have shown that the same catalytic cycle operates for the supported catalyst as in homogeneous solution phase.…”