Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate.
The isomerization of 1-penten-3-ol into 3-pentanone catalyzed by [RuCp(H2O-κO)(PTA)2](CF3SO3) (1CF3SO3) (PTA = 1,3,5-triaza-7-phosphaadamantane) was studied and two watersoluble ruthenium catalyst reaction intermediates were characterized. The main intermediate, the complex [RuCp(exo-η2-1-penten...
| Main Authors: | , , , , |
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| Format: | info:eu-repo/semantics/article |
| Language: | English |
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2024
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| Subjects: | |
| Online Access: | http://hdl.handle.net/10835/15049 |
| _version_ | 1789406512380116992 |
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| author | Scalambra, Franco López-Sánchez, Belen Holzmann, Nicole Bernasconi, Leonardo Romerosa Nievas, Antonio Manuel |
| author_facet | Scalambra, Franco López-Sánchez, Belen Holzmann, Nicole Bernasconi, Leonardo Romerosa Nievas, Antonio Manuel |
| author_sort | Scalambra, Franco |
| collection | DSpace |
| description | The isomerization of 1-penten-3-ol into 3-pentanone
catalyzed by [RuCp(H2O-κO)(PTA)2](CF3SO3) (1CF3SO3) (PTA
= 1,3,5-triaza-7-phosphaadamantane) was studied and two watersoluble
ruthenium catalyst reaction intermediates were characterized.
The main intermediate, the complex [RuCp(exo-η2-1-penten-3-
ol)(PTA)2](CF3SO3)·2H2O (exo-2CF3SO3·2H2O), was isolated
and characterized by NMR in solution and by single-crystal X-ray
diffraction in the solid state, constituting the first example of a fully
characterized complex containing a coordinated η2-allylic alcohol and
the first crystal structure for a water-soluble metal complex
containing a η2-allyl ligand. NMR and Eyring analysis show the
crucial involvement of water molecules both in the transformation of
allylic alcohol into a ketone as well as in the concomitant
isomerization of the exo-coordinated substrate into the endo-conformer. DFT structure and bonding analyses are used to assess
the relative stabilities of the isomers and how the metal drives the electronic distribution on the substrate. |
| format | info:eu-repo/semantics/article |
| id | oai:repositorio.ual.es:10835-15049 |
| institution | Universidad de Cuenca |
| language | English |
| publishDate | 2024 |
| record_format | dspace |
| spelling | oai:repositorio.ual.es:10835-150492024-01-10T09:31:25Z Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. Scalambra, Franco López-Sánchez, Belen Holzmann, Nicole Bernasconi, Leonardo Romerosa Nievas, Antonio Manuel Alcohols Crystal structure Isomerization Ligands Molecular structure The isomerization of 1-penten-3-ol into 3-pentanone catalyzed by [RuCp(H2O-κO)(PTA)2](CF3SO3) (1CF3SO3) (PTA = 1,3,5-triaza-7-phosphaadamantane) was studied and two watersoluble ruthenium catalyst reaction intermediates were characterized. The main intermediate, the complex [RuCp(exo-η2-1-penten-3- ol)(PTA)2](CF3SO3)·2H2O (exo-2CF3SO3·2H2O), was isolated and characterized by NMR in solution and by single-crystal X-ray diffraction in the solid state, constituting the first example of a fully characterized complex containing a coordinated η2-allylic alcohol and the first crystal structure for a water-soluble metal complex containing a η2-allyl ligand. NMR and Eyring analysis show the crucial involvement of water molecules both in the transformation of allylic alcohol into a ketone as well as in the concomitant isomerization of the exo-coordinated substrate into the endo-conformer. DFT structure and bonding analyses are used to assess the relative stabilities of the isomers and how the metal drives the electronic distribution on the substrate. 2024-01-10T09:31:24Z 2024-01-10T09:31:24Z 2020 info:eu-repo/semantics/article http://hdl.handle.net/10835/15049 en Attribution-NonCommercial-NoDerivatives 4.0 Internacional http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess Organometallics 2020, 39, 24, 4491–4499, https://dx.doi.org/10.1021/acs.organomet.0c00585 |
| spellingShingle | Alcohols Crystal structure Isomerization Ligands Molecular structure Scalambra, Franco López-Sánchez, Belen Holzmann, Nicole Bernasconi, Leonardo Romerosa Nievas, Antonio Manuel Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title | Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title_full | Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title_fullStr | Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title_full_unstemmed | Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title_short | Steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| title_sort | steps ahead in understanding the catalytic isomerization mechanism of linear allylic alcohols in water: dynamics, bonding analysis and crystal structure of a 2-allyl-intermediate. |
| topic | Alcohols Crystal structure Isomerization Ligands Molecular structure |
| url | http://hdl.handle.net/10835/15049 |
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