Cargando…
Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity
The fifteen‐membered NNNNN macrocycle Me(5)PACP (Me(5)PACP=1,4,7,10,13‐pentamethyl‐1,4,7,10,13‐pentaazacyclopentadecane) stabilized the [CaH](+) fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium d...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898310/ https://www.ncbi.nlm.nih.gov/pubmed/33185286 http://dx.doi.org/10.1002/chem.202004931 |
_version_ | 1783653836789907456 |
---|---|
author | Höllerhage, Thomas Schuhknecht, Danny Mistry, Alisha Spaniol, Thomas P. Yang, Yan Maron, Laurent Okuda, Jun |
author_facet | Höllerhage, Thomas Schuhknecht, Danny Mistry, Alisha Spaniol, Thomas P. Yang, Yan Maron, Laurent Okuda, Jun |
author_sort | Höllerhage, Thomas |
collection | PubMed |
description | The fifteen‐membered NNNNN macrocycle Me(5)PACP (Me(5)PACP=1,4,7,10,13‐pentamethyl‐1,4,7,10,13‐pentaazacyclopentadecane) stabilized the [CaH](+) fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium dibenzyl with the conjugate acid of Me(5)PACP followed by hydrogenolysis or treating with (n)OctSiH(3) of the intermediate calcium benzyl cation. The calcium hydride catalyzed the hydrogenation and hydrosilylation of unactivated olefins faster than the analogous calcium complex stabilized by the twelve‐membered NNNN macrocycle Me(4)TACD (Me(4)TACD=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane). Kinetic investigations indicate that higher catalytic efficiency for the Me(5)PACP stabilized calcium hydride is due to easier dissociation of the dimer in solution when compared to the Me(4)TACD analogue. |
format | Online Article Text |
id | pubmed-7898310 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-78983102021-03-03 Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity Höllerhage, Thomas Schuhknecht, Danny Mistry, Alisha Spaniol, Thomas P. Yang, Yan Maron, Laurent Okuda, Jun Chemistry Communications The fifteen‐membered NNNNN macrocycle Me(5)PACP (Me(5)PACP=1,4,7,10,13‐pentamethyl‐1,4,7,10,13‐pentaazacyclopentadecane) stabilized the [CaH](+) fragment as a dimer with a distorted pentagonal bipyramidal coordination geometry at calcium. The hydride complex was prepared by protonolysis of calcium dibenzyl with the conjugate acid of Me(5)PACP followed by hydrogenolysis or treating with (n)OctSiH(3) of the intermediate calcium benzyl cation. The calcium hydride catalyzed the hydrogenation and hydrosilylation of unactivated olefins faster than the analogous calcium complex stabilized by the twelve‐membered NNNN macrocycle Me(4)TACD (Me(4)TACD=1,4,7,10‐tetramethyl‐1,4,7,10‐tetraazacyclododecane). Kinetic investigations indicate that higher catalytic efficiency for the Me(5)PACP stabilized calcium hydride is due to easier dissociation of the dimer in solution when compared to the Me(4)TACD analogue. John Wiley and Sons Inc. 2021-01-18 2021-02-10 /pmc/articles/PMC7898310/ /pubmed/33185286 http://dx.doi.org/10.1002/chem.202004931 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Höllerhage, Thomas Schuhknecht, Danny Mistry, Alisha Spaniol, Thomas P. Yang, Yan Maron, Laurent Okuda, Jun Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title | Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title_full | Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title_fullStr | Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title_full_unstemmed | Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title_short | Calcium Hydride Catalysts for Olefin Hydrofunctionalization: Ring‐Size Effect of Macrocyclic Ligands on Activity |
title_sort | calcium hydride catalysts for olefin hydrofunctionalization: ring‐size effect of macrocyclic ligands on activity |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898310/ https://www.ncbi.nlm.nih.gov/pubmed/33185286 http://dx.doi.org/10.1002/chem.202004931 |
work_keys_str_mv | AT hollerhagethomas calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT schuhknechtdanny calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT mistryalisha calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT spaniolthomasp calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT yangyan calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT maronlaurent calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity AT okudajun calciumhydridecatalystsforolefinhydrofunctionalizationringsizeeffectofmacrocyclicligandsonactivity |