Kinetics of hydroformylation of 1-octene in ionic liquid-organic biphasic media using rhodium sulfoxantphos catalyst

Biphasic hydroformylation of 1-octene was performed using rhodium sulfoxantphos catalyst dissolved in [BuPy][BF4] ionic liquid. Preliminary experiments proved this system to retain the catalytic complex within the ionic liquid phase and to maintain a high selectivity towards the linear aldehyde (n:iso ratio of 30) over several cycles. Process parameter investigation showed a first order dependence of the initial rate with respect to the catalyst and 1-octene concentrations, but a more complex behavior with respect to hydrogen (fractional order) and carbon monoxide partial pressures (inhibition at high pressures). Different mathematical models were selected based on the trends observed and evaluated for data fitting. Also, rate models were derived from a proposed mechanism, using Christiansen matrix approach. To calculate concentrations of substrates in the catalytic phase as required by this kinetic modeling, solubility measurements were preformed for the gases (pressure drop technique), as well as for 1-octene and n-nonanal (thermogravimetry analysis)

Rhodium-catalysed hydroformylation of N-(2-propenyl)-β-lactams as a key step in the synthesis of functionalised N-[4-(2-oxoazetidin-1-yl)but-1-enyl]acetamides

Biologically relevant functionalised N-[4-(2-oxoazetidin-1-yl)but-1-enyl]acetamides have been prepared in a two-step approach starting from N-(2-propenyl)-beta-lactams, involving initial rhodium-catalysed hydroformylation followed by subjection of the obtained aldehydes to Staudinger reaction conditions after initial imination

MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

Indexación: Web of Science; Scopus; Scielo.The catalytic activity of systems of type [RuH(CO)(N-N)(PR3)(2)](+) was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO)(3)(PPh3)(2) and RuH3(CO)(PPh3)(2), which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene. Palabras clavehttp://ref.scielo.org/db4yc

Development of covalent triazine frameworks as heterogeneous catalytic supports

Covalent triazine frameworks (CTFs) are established as an emerging class of porous organic polymers with remarkable features such as large surface area and permanent porosity, high thermal and chemical stability, and convenient functionalization that promotes great potential in heterogeneous catalysis. In this article, we systematically present the structural design of CTFs as a versatile scaffold to develop heterogeneous catalysts for a variety of chemical reactions. We mainly focus on the functionalization of CTFs, including their use for incorporating and stabilization of nanoparticles and immobilization of molecular complexes onto the frameworks

Rhodium/phospholane-phosphite catalysts give unusually high regioselectivity in the enantioselective hydroformylation of vinyl arenes

Using the phospholane-phosphite ligand, BOBPHOS, almost perfect regioselectivities and high enantioselectivities (up to 92% ee) are observed in Rh catalysed enantioselective hydroformylation of vinyl arenes. This can be achieved under solvent-free conditions.PostprintPeer reviewe

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*)]

The authors thank the Eastman Chemical Company for funding.Four new phosphine-phosphoramidite bidentate ligands have been synthesised and studied in rhodium-catalysed hydroformylation. Variable temperature NMR studies have been used along with HPIR to investigate the coordination mode of the trigonal bipyramidal complexes formed from [Rh(acac)(CO)2], ligand and syngas. It was found that small changes to the ligand structure have a large effect on the geometry of the active catalytic species. The rhodium catalysts of these new ligands were found to give unusually high iso-selectivity in the hydroformylation of propene and 1-octene.PostprintPeer reviewe

Photochemical preparation of olefin addition catalysts

Novel polymer supported catalysts are prepared by photo-irradiation of low valent transition metal compounds such as Co.sub.2 (CO).sub.8, Rh.sub.4 (CO).sub.12 or Ru.sub.3 (CO).sub.12 in the presence of solid polymers containing amine ligands such as polyvinyl pyridine. Hydroformylation of olefins to aldehydes at ambient conditions has been demonstrated