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Major-minor concept revisited: causes for the of thermodynamically determined intermediate ratios under reaction conditions
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...
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| Published in: | Catalysis science & technology 2023-07, Vol.13 (15), p.4498-455 |
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| container_end_page | 455 |
| container_issue | 15 |
| container_start_page | 4498 |
| container_title | Catalysis science & technology |
| container_volume | 13 |
| creator | Jannsen, Nora Jurrat, Julia Neumann, Helfried Fischer, Christian Thede, Richard Heller, Detlef |
| description | 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.
This work reveals the kinetic reasons for the inversion of the intermediates during catalytic selective reactions by using a model system. |
| doi_str_mv | 10.1039/d3cy00582h |
| format | article |
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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.
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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.
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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.
This work reveals the kinetic reasons for the inversion of the intermediates during catalytic selective reactions by using a model system.</abstract><doi>10.1039/d3cy00582h</doi><tpages>8</tpages></addata></record> |
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| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| title | Major-minor concept revisited: causes for the of thermodynamically determined intermediate ratios under reaction conditions |
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