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Functionalization of Pentaphosphorus Cations by Complexation
Author(s) -
Adhikari Anup K.,
Ziegler Christoph G. P.,
Schwedtmann Kai,
Taube Clemens,
Weigand Jan. J.,
Wolf Robert
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201908998
Subject(s) - chemistry , nucleophile , cationic polymerization , cyclopentadienyl complex , reactivity (psychology) , metal , metathesis , surface modification , medicinal chemistry , stereochemistry , polymer chemistry , organic chemistry , catalysis , polymerization , medicine , polymer , alternative medicine , pathology
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= i Pr and 2,4,6‐Me 3 C 6 H 2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes ( 1‐R , R= i Pr 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= i Pr 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.