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P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes
[L(C) (R)P((PhP)(2)C(2)H(4))][OTf] (4 a,b[OTf]) and [L(C) (iPr)P(PPh(2))(2)][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L(C) (R)P(pyr)(2)][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L(C) (R)=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7065231/ https://www.ncbi.nlm.nih.gov/pubmed/31705596 http://dx.doi.org/10.1002/anie.201911483 |
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author | Taube, Clemens Schwedtmann, Kai Noikham, Medena Somsook, Ekasith Hennersdorf, Felix Wolf, Robert Weigand, Jan J. |
author_facet | Taube, Clemens Schwedtmann, Kai Noikham, Medena Somsook, Ekasith Hennersdorf, Felix Wolf, Robert Weigand, Jan J. |
author_sort | Taube, Clemens |
collection | PubMed |
description | [L(C) (R)P((PhP)(2)C(2)H(4))][OTf] (4 a,b[OTf]) and [L(C) (iPr)P(PPh(2))(2)][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L(C) (R)P(pyr)(2)][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L(C) (R)=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C(2)H(4)P(H)Ph) and Ph(2)PH. A stepwise double P−N/P−P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph(2)P)(2)(L(C) (Me)P)(2)][OTf](2) (7 a[OTf](2)) is observed when reacting 3 a[OTf] with diphosphane P(2)Ph(4). The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH(3)CN)(4)]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph(2)PPL(C) (iPr))Au}(4)][OTf](4) (9[OTf](4)) was unexpectedly formed as a result of a chloride‐induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH(3)CN)(3)][OTf](2) (M=Cu, Ag) (10[OTf](2), 11[OTf](2)). |
format | Online Article Text |
id | pubmed-7065231 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-70652312020-03-16 P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes Taube, Clemens Schwedtmann, Kai Noikham, Medena Somsook, Ekasith Hennersdorf, Felix Wolf, Robert Weigand, Jan J. Angew Chem Int Ed Engl Research Articles [L(C) (R)P((PhP)(2)C(2)H(4))][OTf] (4 a,b[OTf]) and [L(C) (iPr)P(PPh(2))(2)][OTf] (5 b[OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L(C) (R)P(pyr)(2)][OTf] (3 a,b[OTf]; a: R=Me, b=iPr; L(C) (R)=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C(2)H(4)P(H)Ph) and Ph(2)PH. A stepwise double P−N/P−P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph(2)P)(2)(L(C) (Me)P)(2)][OTf](2) (7 a[OTf](2)) is observed when reacting 3 a[OTf] with diphosphane P(2)Ph(4). The coordination ability of 5 b[OTf] was probed with selected coinage metal salts [Cu(CH(3)CN)(4)]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph(2)PPL(C) (iPr))Au}(4)][OTf](4) (9[OTf](4)) was unexpectedly formed as a result of a chloride‐induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [(5 b)M(CH(3)CN)(3)][OTf](2) (M=Cu, Ag) (10[OTf](2), 11[OTf](2)). John Wiley and Sons Inc. 2019-12-30 2020-02-24 /pmc/articles/PMC7065231/ /pubmed/31705596 http://dx.doi.org/10.1002/anie.201911483 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Research Articles Taube, Clemens Schwedtmann, Kai Noikham, Medena Somsook, Ekasith Hennersdorf, Felix Wolf, Robert Weigand, Jan J. P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title | P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title_full | P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title_fullStr | P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title_full_unstemmed | P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title_short | P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes |
title_sort | p−p condensation and p−n/p−p bond metathesis: facile synthesis of cationic tri‐ and tetraphosphanes |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7065231/ https://www.ncbi.nlm.nih.gov/pubmed/31705596 http://dx.doi.org/10.1002/anie.201911483 |
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