Mapping‐Out Catalytic Processes in a Metal–Organic Framework with Single‐Crystal X‐ray Crystallography

Abstract

Single-crystal X-ray crystallography is employed to characterize the reaction species of af ull catalytic carbonylation cycle within aM n II -based metal-organic framework (MOF) material. The structural insights explain why the Rh metalated MOF is catalytically competent towardt he carbonylation of MeBr but only affords stoichiometric turn-over in the case of MeI. This work highlights the capability of MOFs to act as platform materials for studying single-site catalysis in heterogeneous systems.

Isolating reactive metal-based species in Metal–Organic Frameworks – viable strategies and opportunities

“…Recent advances have realised this potential, most notably using the Mn-derived framework MnMOF-1 ([Mn 3 (L) 2 L 0 ], where L ¼ bis(4-carboxyphenyl-3,5-dimethyl-pyrazol-1-yl)methane). 141,142 Compared to UiO-67-bpy, this framework exhibits particular qualities as a host for post-synthetic metalation chemistry (Fig. 6).…”

“…As a result, the material acts as a crystalline matrix within which coordination chemistry can be studied in exemplary detail. [142][143][144][145] Reactions involving the octahedral-tetrahedral interconversion of Co(II) complexes 141 and sequential anion exchange and [2 + 3]-cycloaddition chemistry of a Mn(I) complex 145 have all been studied inside MnMOF-1 using X-ray crystallography. Furthermore, studying reactivity using MnMOF-1 has recently been extended to organometallic catalysis.…”

“…Furthermore, studying reactivity using MnMOF-1 has recently been extended to organometallic catalysis. 142 The Monsanto acetic acid synthesis is an important industrial chemical processes, performed using homogenous Rh(I) carbonyl catalysts. 146 The mechanism involves oxidative addition of MeI to the metal centre, migratory insertion of the methyl fragment into the M-CO bond and reductive elimination of acetyl iodide to regenerate the square planar catalyst.…”

Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates

“…We have recently reported the synthesis, using single-crystal to single-crystal solid/gas techniques, 41 , 50 – 53 of well-defined sigma-alkane complexes, 54 , 55 typified by [Rh(R 2 PCH 2 CH 2 PR 2 )(η 2 η 2 -NBA)][BAr F 4 ] [R = i Bu, Cyp, Cy; NBA = norbornane; Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ]; Scheme 2a . 56 – 59 The key to these complexes' relative stability in the solid-state is the arrangement of [BAr F 4 ] – anions that provide a well-defined cavity ( i.e.…”

Co2 and Co3 Mixed Cluster Secondary Building Unit Approach toward a Three-Dimensional Metal-Organic Framework with Permanent Porosity

“…Creating large and permanent porosity in metal-organic frameworks (MOFs) is a prerequisite for particular applications, such as catalysis [ 1 , 2 , 3 , 4 , 5 , 6 , 7 ], drug delivery [ 8 , 9 , 10 , 11 , 12 , 13 ], as well as the study of fundamental host-guest phenomena, including enzyme [ 14 , 15 , 16 , 17 ], protein [ 18 ], water [ 19 , 20 , 21 , 22 ], and nanoparticle [ 23 , 24 , 25 , 26 , 27 , 28 , 29 ] encapsulation. However, during the formation of MOFs with targeted porosity, there exists a trade-off between the pore size and framework stability, viz., the shorter ligands generally support stable MOFs with limited porosity, while the longer ligands prefer porous frameworks with limited scaffold stability [ 30 ].…”