Functionalization of Pentaphosphorus Cations by Complexation

The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P(5)R(2)](+) cations with cyclopentadienyl metal complexes. The reaction of [Cp(Ar)Fe(μ‐Br)](2) (Cp(Ar)=C(5)(C(6)H(4)‐...

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Autores principales: Adhikari, Anup K., Ziegler, Christoph G. P., Schwedtmann, Kai, Taube, Clemens, Weigand, Jan. J., Wolf, Robert
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/PMC6916545/
https://www.ncbi.nlm.nih.gov/pubmed/31559678
http://dx.doi.org/10.1002/anie.201908998
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author Adhikari, Anup K.
Ziegler, Christoph G. P.
Schwedtmann, Kai
Taube, Clemens
Weigand, Jan. J.
Wolf, Robert
author_facet Adhikari, Anup K.
Ziegler, Christoph G. P.
Schwedtmann, Kai
Taube, Clemens
Weigand, Jan. J.
Wolf, Robert
author_sort Adhikari, Anup K.
collection PubMed
description The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P(5)R(2)](+) cations with cyclopentadienyl metal complexes. The reaction of [Cp(Ar)Fe(μ‐Br)](2) (Cp(Ar)=C(5)(C(6)H(4)‐4‐Et)(5)) with [P(5)R(2)][GaCl(4)] (R=iPr and 2,4,6‐Me(3)C(6)H(2) (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1‐R, R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[Cp(Ar)] and [P(5)R(2)][GaCl(4)]. The cationic complexes [Cp(Ar)Co(η(4)‐P(5)R(2))][GaCl(4)] (2‐R[GaCl(4)], R=iPr and Cy) and [(Cp(Ar)Ni)(2)(η(3:3)‐P(5)R(2))][GaCl(4)] (3‐R[GaCl(4)]) were obtained from [P(5)R(2)][GaCl(4)] and [Cp(Ar)M(μ‐Br)](2) (M=Co and Ni) as well as by using low‐valent “Cp(Ar)M(I)” sources. Anion metathesis of 2‐R[GaCl(4)] and 3‐R[GaCl(4)] was achieved with Na[BArF(24)]. The P(5) framework of the resulting salts 2‐R[BArF(24)] can be further functionalized with nucleophiles. Thus reactions with [Et(4)N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl.
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spelling pubmed-69165452019-12-23 Functionalization of Pentaphosphorus Cations by Complexation Adhikari, Anup K. Ziegler, Christoph G. P. Schwedtmann, Kai Taube, Clemens Weigand, Jan. J. Wolf, Robert Angew Chem Int Ed Engl Research Articles The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P(5)R(2)](+) cations with cyclopentadienyl metal complexes. The reaction of [Cp(Ar)Fe(μ‐Br)](2) (Cp(Ar)=C(5)(C(6)H(4)‐4‐Et)(5)) with [P(5)R(2)][GaCl(4)] (R=iPr and 2,4,6‐Me(3)C(6)H(2) (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1‐R, R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[Cp(Ar)] and [P(5)R(2)][GaCl(4)]. The cationic complexes [Cp(Ar)Co(η(4)‐P(5)R(2))][GaCl(4)] (2‐R[GaCl(4)], R=iPr and Cy) and [(Cp(Ar)Ni)(2)(η(3:3)‐P(5)R(2))][GaCl(4)] (3‐R[GaCl(4)]) were obtained from [P(5)R(2)][GaCl(4)] and [Cp(Ar)M(μ‐Br)](2) (M=Co and Ni) as well as by using low‐valent “Cp(Ar)M(I)” sources. Anion metathesis of 2‐R[GaCl(4)] and 3‐R[GaCl(4)] was achieved with Na[BArF(24)]. The P(5) framework of the resulting salts 2‐R[BArF(24)] can be further functionalized with nucleophiles. Thus reactions with [Et(4)N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl. John Wiley and Sons Inc. 2019-11-06 2019-12-16 /pmc/articles/PMC6916545/ /pubmed/31559678 http://dx.doi.org/10.1002/anie.201908998 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/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
spellingShingle Research Articles
Adhikari, Anup K.
Ziegler, Christoph G. P.
Schwedtmann, Kai
Taube, Clemens
Weigand, Jan. J.
Wolf, Robert
Functionalization of Pentaphosphorus Cations by Complexation
title Functionalization of Pentaphosphorus Cations by Complexation
title_full Functionalization of Pentaphosphorus Cations by Complexation
title_fullStr Functionalization of Pentaphosphorus Cations by Complexation
title_full_unstemmed Functionalization of Pentaphosphorus Cations by Complexation
title_short Functionalization of Pentaphosphorus Cations by Complexation
title_sort functionalization of pentaphosphorus cations by complexation
topic Research Articles
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916545/
https://www.ncbi.nlm.nih.gov/pubmed/31559678
http://dx.doi.org/10.1002/anie.201908998
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