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Comparison of the Full Catalytic Cycle of Hydroformylation Mediated by Mono‐ and Bis‐Ligated Triphenylphosphine–Rhodium Complexes by Using DFT Calculations
Author(s) -
Jacobs Ivo,
de Bruin Bas,
Reek Joost N. H.
Publication year - 2015
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201500087
Subject(s) - hydroformylation , rhodium , catalysis , triphenylphosphine , chemistry , catalytic cycle , reactivity (psychology) , ligand (biochemistry) , photochemistry , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology
The coordination mode of triphenylphosphine to rhodium is considered to be important for the outcome of hydroformylation catalysis. The difference in reactivity between mono‐ and bis‐ligated rhodium species has not been investigated systematically, mostly because it is impossible to obtain pure mono‐ligated rhodium under hydroformylation conditions. Therefore, we performed detailed computational studies to get an insight into the effect of the coordination of triphenylphosphine to rhodium on hydroformylation catalysis. The DFT‐calculated catalytic pathway of the monophosphine‐based catalyst shows a lower free energy barrier (24.5 kcal mol −1 ) compared to the pathway of the bisphosphine catalyst (28.9 kcal mol −1 ). This confirms that monophosphine catalysts have an intrinsically higher activity than bisphosphine catalysts and indicates that the rate enhancement seen with the tetraphenylporphyrin‐based catalyst reported by our group previously is at least partly due to the monocoordination enforced by this encapsulating ligand.