Massively parallel entropy based pattern recognition for system identification in catalytic binuclear elimination reaction

Abstract

Recently, it was found that the simultaneous use of both Rh 4(CO) 12 and HRe(CO) 5 in the homogeneous catalytic hydroformylation of cyclopentene to cyclopentane carboxaldehyde, leads to a dramatic increase in rate of reaction. Two experimental designs were planned and two sets of in-situ spectroscopic experiments performed using FTIR. The first experimental design without organic substrate added, and the second was performed in n-hexane solvent at 278-303K and 0.2-8.0 MPa total pressure using CO and H 2. A total of circa 4000 spectra were collected spectra on the interval 1550 2500cm -1. Both of the data matrices were analyzed using SVD and our group-developed software tools including BTEM to solve the algebraic inverse problem and differential inverse problem. In particular, SVD was performed and circa s=10 spectral patterns were recovered using exhaustive global searches using BTEM. The pure components were reconstructed, the mole numbers of each species were obtained and the reaction stoichiometry and reaction contents were determined. From the first experimental design, one new previously unknown species RhRe(CO) 9 was identified. The second set data showed a very significant increase in aldehyde formation and TOF was observed in some experiments when both rhodium carbonyl and rhenium carbonyl complexes were used simultaneously. The kinetics of product formation shows a distinct linear-bilinear form in observables. Taken together, the results again support the existence of catalytic binuclear elimination. The new mechanism is described in detail.