A modular family of phosphine-phosphoramidite ligands and their hydroformylation catalysts: steric tuning impacts upon the coordination geometry of trigonal bipyramidal complexes of type [Rh(H)(CO)₂(P^P*)]

Abstract

Branched aldehyde selectivity above 50% in hydroformylation of propene and 1-octene.

Heterogenized Molecular Rhodium Phosphine Catalyst within Metal-Organic Framework for Ethylene Hydroformylation

“…In the case of MOF-808-2.0DPPB-Rh, the Rh(acac) cannot be considered as a catalytically active species, in contrast to RhH, according to reported hydroformylation catalytic mechanism. 70,71 Thus, under gas mixture stream at 1 atm and 70°C, the removal of the acac group took place leading to Rh gem-dicarbonyl species similar to those observed for the MOF-808-2.0DPPB-RhH. This species then reacts similarly with ethylene as in the case of the RhH precursor, with somewhat lower TOF (2.0 h -1 ) (see Figure S67, Right)).…”

Isoselective Hydroformylation of Propylene by Iodide‐Assisted Palladium Catalysis

“…The commercial processes occur in the presence of either Rh or Co catalysts whose inherent selectivity favors the formation of n ‐butanal over isobutanal [2–4] . The increasing demand for isobutanal‐derived materials, such as plasticizers, coatings, solvents, cleaners, food additives, or extractants for pharmaceutical products, as well as the unmatched challenge of developing catalysts featuring the isoselectivity, have driven significant research [5–20] . However, limited progress has been achieved thus far and no methods have been commercialized.…”

“…[2][3][4] The increasing demand for isobutanal-derived materials, such as plasticizers, coatings, solvents, cleaners, food additives, or extractants for pharmaceutical products, as well as the unmatched challenge of developing catalysts featuring the isoselectivity, have driven significant research. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] However, limited progress has been achieved thus far and no methods have been commercialized. The main approach has been the development of tailored phosphorus ligands of the Rh catalysts.…”

Branched-Selective Hydroformylation of Nonactivated Olefins Using an N-Triphos/Rh Catalyst

“…To date, few examples of catalyst systems capable of performing branched-selective hydroformylation of nonactivated terminal olefins have been reported . Two notable examples of highly selective systems that represent the current state-of-the-art for this reaction are a rhodium encapsulation complex reported by Reek and co-workers and a Rh/BOBPHOS system reported by Clarke and co-workers. , The former is constructed from a tripyridylphosphine ligand that coordinates to a rhodium center through phosphorus and three metallo-porphyrin units via the three nitrogens within the pyridyl moieties of the ligand (Chart , bottom left).…”