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)‐...
Autores principales: | , , , , , |
---|---|
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 |
_version_ | 1783480252861775872 |
---|---|
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. |
format | Online Article Text |
id | pubmed-6916545 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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 |
work_keys_str_mv | AT adhikarianupk functionalizationofpentaphosphoruscationsbycomplexation AT zieglerchristophgp functionalizationofpentaphosphoruscationsbycomplexation AT schwedtmannkai functionalizationofpentaphosphoruscationsbycomplexation AT taubeclemens functionalizationofpentaphosphoruscationsbycomplexation AT weigandjanj functionalizationofpentaphosphoruscationsbycomplexation AT wolfrobert functionalizationofpentaphosphoruscationsbycomplexation |