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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‐...

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Autores principales: Taube, Clemens, Schwedtmann, Kai, Noikham, Medena, Somsook, Ekasith, Hennersdorf, Felix, Wolf, Robert, Weigand, Jan J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
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)).
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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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