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Realistic energy surfaces for real-world systems : an IMOMO CCSD(T):DFT scheme for rhodium-catalyzed hydroformylation with the 6-DPPon ligand

Gellrich, Urs and Himmel, Daniel and Meuwly, Markus and Breit, Bernhard. (2013) Realistic energy surfaces for real-world systems : an IMOMO CCSD(T):DFT scheme for rhodium-catalyzed hydroformylation with the 6-DPPon ligand. Chemistry, 19 (48). pp. 16272-16281.

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Official URL: http://edoc.unibas.ch/dok/A6223430

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Abstract

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-(2H)-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 PH3 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.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Meuwly)
UniBasel Contributors:Meuwly, Markus
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Wiley
ISSN:0947-6539
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:07 Dec 2016 12:20
Deposited On:27 Mar 2014 13:12

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