Premium
Realistic Energy Surfaces for Real‐World Systems: An IMOMO CCSD(T):DFT Scheme for Rhodium‐Catalyzed Hydroformylation with the 6‐DPPon Ligand
Author(s) -
Gellrich Urs,
Himmel Daniel,
Meuwly Markus,
Breit Bernhard
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201302132
Subject(s) - hydroformylation , rhodium , scheme (mathematics) , catalysis , ligand (biochemistry) , chemistry , computational chemistry , mathematics , organic chemistry , mathematical analysis , biochemistry , receptor
The hydroformylation of terminal alkenes is one of the most important homogeneously catalyzed processes in industry, and the atomistic understanding of this reaction has attracted enormous interest in the past. Herein, the whole catalytic cycle for rhodium‐catalyzed hydroformylation with the 6‐diphenylphosphinopyridine‐(2 H )‐1‐one (6‐DPPon) ligand 1 was studied. This catalytic transformation is challenging to describe computationally, since two requirements must be met: 1) changes in the hydrogen‐bond network must be modeled accurately and 2) bond‐formation/bond‐breaking processes in the coordination sphere of the rhodium center must be calculated accurately. Depending on the functionals used (BP86, B3LYP), the results were found to differ strongly. Therefore, the complete cycle was calculated by using highly accurate CCSD(T) computations for a PH 3 model ligand. By applying an integrated molecular orbital plus molecular orbital (IMOMO) method consisting of CCSD(T) as high level and DFT as low‐level method, excellent agreement between the two functionals was achieved. To further test the reliability of the calculations, the energetic‐span model was used to compare experimentally derived and computed activation barriers. The accuracy of the new IMOMO method apparently makes it possible to predict the catalytic potential of real‐world systems.