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Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium
The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange w...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8161683/ https://www.ncbi.nlm.nih.gov/pubmed/34094222 http://dx.doi.org/10.1039/d0sc03773g |
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author | Birchall, Nicholas Feil, Christoph M. Gediga, Michael Nieger, Martin Gudat, Dietrich |
author_facet | Birchall, Nicholas Feil, Christoph M. Gediga, Michael Nieger, Martin Gudat, Dietrich |
author_sort | Birchall, Nicholas |
collection | PubMed |
description | The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange with gaseous H(2) and D(2). Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2) cleavage across a 3d M[double bond, length as m-dash]P bond. The same species is also accessible via stepwise H(+)/H(−) transfer to the bis-phosphenium complex, and releases H(2) upon heating or irradiation. Dihydrogen transfer from the H(2)-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex. |
format | Online Article Text |
id | pubmed-8161683 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-81616832021-06-04 Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium Birchall, Nicholas Feil, Christoph M. Gediga, Michael Nieger, Martin Gudat, Dietrich Chem Sci Chemistry The reversible reaction of H(2) with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2) and yields a spectroscopically detectable phosphenium-stabilized (σ–H(2))-complex, readily showing exchange with gaseous H(2) and D(2). Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2) cleavage across a 3d M[double bond, length as m-dash]P bond. The same species is also accessible via stepwise H(+)/H(−) transfer to the bis-phosphenium complex, and releases H(2) upon heating or irradiation. Dihydrogen transfer from the H(2)-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex. The Royal Society of Chemistry 2020-08-21 /pmc/articles/PMC8161683/ /pubmed/34094222 http://dx.doi.org/10.1039/d0sc03773g Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Birchall, Nicholas Feil, Christoph M. Gediga, Michael Nieger, Martin Gudat, Dietrich Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title | Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title_full | Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title_fullStr | Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title_full_unstemmed | Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title_short | Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
title_sort | reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8161683/ https://www.ncbi.nlm.nih.gov/pubmed/34094222 http://dx.doi.org/10.1039/d0sc03773g |
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