In:
Catalysis Science & Technology, Royal Society of Chemistry (RSC), Vol. 13, No. 15 ( 2023), p. 4498-4505
Abstract:
The present work deals with the kinetic reasons for the inversion of the intermediates during catalytic selective reactions. By using a model system, typical ratios between diastereomer “catalyst–substrate” complexes are simulated by stable diolefin complexes [Rh(PP)(diolefin)]BF 4 of NBD (norborna-2,5-diene) and COD (( Z , Z )-cycloocta-1,5-diene). The detailed kinetic study demonstrates figuratively how the thermodynamically dominant species during the catalysis is not necessarily the major “catalyst–substrate” complex. By determination of all rate constants involved, the reasons for the unusual experimental behaviour of intermediate reversal under reaction conditions are depicted. The experimentally detected effect on a model reaction is of great importance for the explanation of the direction of, e.g. , stereoselection and considerably extends the mechanistic understanding of selective reactions.
Type of Medium:
Online Resource
ISSN:
2044-4753
,
2044-4761
Language:
English
Publisher:
Royal Society of Chemistry (RSC)
Publication Date:
2023
detail.hit.zdb_id:
2595090-3
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