Ultrastable 3V-PPh3 polymers supported single Rh sites for fixed-bed hydroformylation of olefins

Porous Organic Polymers Containing Active Metal Centers as Catalysts for Synthetic Organic Chemistry

“…30,32,33,34,35,36 The solvent is often N,Ndimethylformamide (DMF), tetrahydrofuran (THF), or chlorobenzene, but solvents like ethyl acetate 33 , 1-methyl-2-pyrrolidinone 37,38 , and mixtures such as benzotrifluoride/water have also been used. The monomers used for this kind of polymerization are usually inspired by phosphineor nitrogen-based ligands such as PPh3 30,40 , BINAP 34 or bipyridine (Figure 4). Divinylbenzene, styrene, and derivatives of styrene are common co-building blocks for radical polymerizations.…”

“…126,127 Interestingly, Ding, Liu, and coworkers demonstrated the successful application of a Rh-PPh3-POP for continuous flow hydroformylation of ethylene in a fixed-bed reactor. 40 During the stability test, a TOF of approximately 4500 h -1 was maintained over 1000 hours on stream with a corresponding 96% selectivity for propanal. Minimal leaching was detected during the stability test as the rhodium content only decreased from 0.125 wt% in the fresh catalyst to 0.121 wt% at the end of the test.…”

Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds

“…The Rh/POL-PPh 3 polymer complex actively catalyzed hydroformylation of ethylene, octene-1 and dodecene-1 at 120°С under the syngas pressure of 1.0 MPa. In all the cases aldehyde yields were close to 90% [76]. POLYMERIC HETEROGENEOUS CATALYSTS IN THE HYDROFORMYLATION An alternative way of synthesis of the same catalyst, which includes preliminary formation of the Rh(3v-PPh 3 )(CO)(acac) complex, which is then subjected to solvothermal radical polymerization, results in a material wherein rhodium atoms are inside the volume of the polymer rather than on the surface, unlike the previous case (Fig.…”

“…The required porosity is achieved by using monomers, which form a rigid porous polymeric structure under the polymerization conditions; thus the proper choice of a building block is critical for their synthesis. The methods for the synthesis of porous organic polymer carriers based on triphenylphosphine POL-PPh 3 (where POL stands for porous organic ligand) were developed for the fi rst time in 2014 [76]. Tris(4-vinylphenyl)phosphine (3vPPh 3 ) was used as the starting monomer, and POL-PPh 3 obtained through polymerization of that monomer had a high surface area (1086 m 2 /g), structural porosity, and high thermal stability (up to 440°C).…”

Highly Efficient Heterogeneous Pd@POPs Catalyst for the N-Formylation of Amine and CO2

“…Our group has been committed to the preparation and application of triphenylphosphinebased porous organic polymers. Rh/POL-PPh 3 [22], Rh/CPOL-BP&PPh 3 [23], and Rh/CPOL-BP&P(OPh) 3 [24] have been applied in the hydroformylation of ethylene, propylene, and butene, respectively. These catalysts exhibited exciting catalytic activity and stability.…”