Concomitant use of liquid–liquid batch and continuous plug flow reactors for kinetic model discrimination. Application to the Rh/TPPTS catalysed reduction of the C–C double bond in dimethylitaconate

Kinetic and Mechanistic Study of the H-Transfer Reduction of Dimethyl Itaconate by a Rh/TPPTS Catalyst under Biphasic Conditions: Evidence for a Rhodametallacycle Intermediate

“…[11] A previous study [7] allowed the extraction of an activation energy of 71 kJ⋅mol -1 , in good agreement with those reported for other hydrogen transfer reductions of olefins. [12] The study also led us to propose the semi-empirical rate model of Equation 3, taking into account all the results obtained during that preliminary study.…”

“…-Partition isotherms determination: The experimental procedure for determining partition isotherms has already been described in a previous paper. [7] -Kinetic studies in a well mixed batch reactor: All the details have already been described in a previous paper. [7] The reduction of dimethyl itaconate (DMI) was performed under a range of conditions, given in Table 2.…”

“…As these reactions catalysed by chiral diphosphane complexes in aqueous medium are generally very complex, the racemic reduction of a prochiral substrate with a nonchiral monophosphane ligand was first studied. The kinetics of this reaction using dimethyl itaconate as a substrate and Rh/TPPTS as a catalytic complex were further investigated, [7] and labelling studies were undertaken in order to understand the mechanism and propose a catalytic cycle reflecting both the kinetic and mechanistic studies.…”

Kinetic Study of Homogeneous Alkene Hydrogenation by Model Discrimination

“…[3] A thorough kinetic description of catalytic systems allows optimization of reaction conditions in order to improve the stability and activity of the catalyst as expressed by total turnover number and turnover frequencies, respectively. [3] Whereas a number of studies on the effect of hydrogen pressure and mass-transfer on the selectivity of homogeneous catalytic hydrogenations have been reported, [4] kinetic studies are rare. [3,5] Description of the kinetics of homogeneous catalysis faces several difficulties.…”

“…[3] Whereas a number of studies on the effect of hydrogen pressure and mass-transfer on the selectivity of homogeneous catalytic hydrogenations have been reported, [4] kinetic studies are rare. [3,5] Description of the kinetics of homogeneous catalysis faces several difficulties. The use of initial rate measurements is often problematic as the true catalyst is first formed from a precatalyst species.…”