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DFT study of the full catalytic cycle for the propene hydroformylation catalyzed by a heterobimetallic HPt(SnCl 3 )(PH 3 ) 2 model catalyst
Author(s) -
da Silva Júlio C. S.,
Dias Roberta P.,
de Almeida Wagner B.,
Rocha Willian R.
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21483
Subject(s) - hydroformylation , catalytic cycle , catalysis , chemistry , propene , olefin fiber , polarizable continuum model , computational chemistry , regioselectivity , basis set , rhodium , density functional theory , solvent , solvent effects , organic chemistry
Abstract DFT calculations were carried out to study the full catalytic cycle for the hydroformylation of propene, catalyzed by the heterobimetallic model catalyst trans ‐Pt(H)(PH 3 ) 2 (SnCl 3 ). Before the study of the full catalytic cycle, the performance of six pure GGA, one GGA with inclusion of dispersion corrections, four hybrid‐GGA, and three meta‐GGA exchange correlation functional to describe a model reaction promoted by Pt‐Sn catalyst were assessed. It is shown that the BP86 and GPW91 functionals, using extended basis set, provides reliable energetic results when compared with the CCSD(T) calculations. All intermediates and transition states along the elementary steps of the entire catalytic cycle were located and the energies involved in the catalytic cycle calculated using BP86 functional. The solvent effects along the entire catalytic cycle were evaluated using the polarizable continuum model. In contrast with the rhodium catalysts, the regioselectivity of the hydroformylation is set at the carbonylation step. The hydrogenolysis is the rate determining step of the entire cycle, with the activation energy of ∼21 kcal mol −1 in agreement with the experimental value of ∼25 kcal mol −1 . The trans effect of the SnCl 3 −ligand seems to be pronounced only in the first step of the catalytic cycle, facilitating the insertion of the olefin into the PtH bond trans to it. The analysis of the stationary points obtained along each elementary step of the catalytic cycle is carried out separately and discussed. The BP86/cc‐pVTZ/SBKJC results shows that the pathway leading to the linear aldehyde is preferred, being in agreement with the experimental findings. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010