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Selective Transfer Semihydrogenation of Alkynes Catalyzed by an Iron PCP Pincer Alkyl Complex
[Image: see text] Two bench-stable Fe(II) alkyl complexes [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(R)] (R = CH(2)CH(2)CH(3), CH(3)) were obtained by the treatment of [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(H)] with NaNH(2) and subsequent addition of CH(3)CH(2)CH(2)Br and CH(3)I, respectively. The reaction proceeds via the a...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10629171/ https://www.ncbi.nlm.nih.gov/pubmed/37942266 http://dx.doi.org/10.1021/acscatal.3c04156 |
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author | Schratzberger, Heiko Stöger, Berthold Veiros, Luis F. Kirchner, Karl |
author_facet | Schratzberger, Heiko Stöger, Berthold Veiros, Luis F. Kirchner, Karl |
author_sort | Schratzberger, Heiko |
collection | PubMed |
description | [Image: see text] Two bench-stable Fe(II) alkyl complexes [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(R)] (R = CH(2)CH(2)CH(3), CH(3)) were obtained by the treatment of [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(H)] with NaNH(2) and subsequent addition of CH(3)CH(2)CH(2)Br and CH(3)I, respectively. The reaction proceeds via the anionic Fe(0) intermediate Na[Fe(κ(3)PCP-PCP-iPr)(CO)(2)]. The catalytic performance of both alkyl complexes was investigated for the transfer hydrogenation of terminal and internal alkynes utilizing PhSiH(3) and iPrOH as a hydrogen source. Precatalyst activation is initiated by migration of the alkyl ligand to the carbonyl C atom of an adjacent CO ligand. In agreement with previous findings, the rate of alkyl migration follows the order nPr > Me. Accordingly, [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(CH(2)CH(2)CH(3))] is the more active catalyst. The reaction takes place at 25 °C with a catalyst loading of 0.5 mol%. There was no overhydrogenation, and in the case of internal alkynes, exclusively, Z-alkenes are formed. The implemented protocol tolerates a variety of electron-donating and electron-withdrawing functional groups including halides, nitriles, unprotected amines, and heterocycles. Mechanistic investigations including deuterium labeling studies and DFT calculations were undertaken to provide a reasonable reaction mechanism. |
format | Online Article Text |
id | pubmed-10629171 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-106291712023-11-08 Selective Transfer Semihydrogenation of Alkynes Catalyzed by an Iron PCP Pincer Alkyl Complex Schratzberger, Heiko Stöger, Berthold Veiros, Luis F. Kirchner, Karl ACS Catal [Image: see text] Two bench-stable Fe(II) alkyl complexes [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(R)] (R = CH(2)CH(2)CH(3), CH(3)) were obtained by the treatment of [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(H)] with NaNH(2) and subsequent addition of CH(3)CH(2)CH(2)Br and CH(3)I, respectively. The reaction proceeds via the anionic Fe(0) intermediate Na[Fe(κ(3)PCP-PCP-iPr)(CO)(2)]. The catalytic performance of both alkyl complexes was investigated for the transfer hydrogenation of terminal and internal alkynes utilizing PhSiH(3) and iPrOH as a hydrogen source. Precatalyst activation is initiated by migration of the alkyl ligand to the carbonyl C atom of an adjacent CO ligand. In agreement with previous findings, the rate of alkyl migration follows the order nPr > Me. Accordingly, [Fe(κ(3)PCP-PCP-iPr)(CO)(2)(CH(2)CH(2)CH(3))] is the more active catalyst. The reaction takes place at 25 °C with a catalyst loading of 0.5 mol%. There was no overhydrogenation, and in the case of internal alkynes, exclusively, Z-alkenes are formed. The implemented protocol tolerates a variety of electron-donating and electron-withdrawing functional groups including halides, nitriles, unprotected amines, and heterocycles. Mechanistic investigations including deuterium labeling studies and DFT calculations were undertaken to provide a reasonable reaction mechanism. American Chemical Society 2023-10-17 /pmc/articles/PMC10629171/ /pubmed/37942266 http://dx.doi.org/10.1021/acscatal.3c04156 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Schratzberger, Heiko Stöger, Berthold Veiros, Luis F. Kirchner, Karl Selective Transfer Semihydrogenation of Alkynes Catalyzed by an Iron PCP Pincer Alkyl Complex |
title | Selective Transfer Semihydrogenation of Alkynes Catalyzed
by an Iron PCP Pincer Alkyl Complex |
title_full | Selective Transfer Semihydrogenation of Alkynes Catalyzed
by an Iron PCP Pincer Alkyl Complex |
title_fullStr | Selective Transfer Semihydrogenation of Alkynes Catalyzed
by an Iron PCP Pincer Alkyl Complex |
title_full_unstemmed | Selective Transfer Semihydrogenation of Alkynes Catalyzed
by an Iron PCP Pincer Alkyl Complex |
title_short | Selective Transfer Semihydrogenation of Alkynes Catalyzed
by an Iron PCP Pincer Alkyl Complex |
title_sort | selective transfer semihydrogenation of alkynes catalyzed
by an iron pcp pincer alkyl complex |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10629171/ https://www.ncbi.nlm.nih.gov/pubmed/37942266 http://dx.doi.org/10.1021/acscatal.3c04156 |
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