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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...

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Autores principales: Höllerhage, Thomas, Schuhknecht, Danny, Mistry, Alisha, Spaniol, Thomas P., Yang, Yan, Maron, Laurent, Okuda, Jun
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
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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.
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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
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