Adhikari, Anup K. and Ziegler, Christoph G. P. and Schwedtmann, Kai and Taube, Clemens and Weigand, Jan J. and Wolf, Robert (2019) Functionalization of Pentaphosphorus Cations by Complexation. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 58 (51). pp. 18584-18590. ISSN 1433-7851, 1521-3773
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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 [P5R2](+) cations with cyclopentadienyl metal complexes. The reaction of [(CpFe)-Fe-Ar(mu-Br)](2) (Cp-Ar=C-5(C6H4-4-Et)(5)) with [P5R2][GaCl4] (R=iPr and 2,4,6-Me3C6H2 (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 [P5R2][GaCl4]. The cationic complexes [(CpCo)-Co-Ar(eta(4)-P5R2)][GaCl4] (2-R[GaCl4], R=iPr and Cy) and [((CpNi)-Ni-Ar)(2)(eta(3:3)-P5R2)][GaCl4] (3-R[GaCl4]) were obtained from [P5R2][GaCl4] and [(CpM)-M-Ar(mu-Br)](2) (M=Co and Ni) as well as by using low-valent "(CpMI)-M-Ar" sources. Anion metathesis of 2-R[GaCl4] and 3-R[GaCl4] was achieved with Na[BArF24]. The P-5 framework of the resulting salts 2-R[BArF24] can be further functionalized with nucleophiles. Thus reactions with [Et4N]X (X=CN and Cl) give unprecedented cyano- and chloro-functionalized complexes, while organo-functionalization was achieved with CyMgCl.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COORDINATED WHITE PHOSPHORUS; P-4 ACTIVATION; LEWIS-ACID; P5X2+ X; P BOND; LIGAND; CHEMISTRY; PENTAPHOSPHAFERROCENE; REACTIVITY; RHODIUM; cobalt; coordination compounds; nickel; P ligands; phosphorus |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf |
| Depositing User: | Petra Gürster |
| Date Deposited: | 07 Apr 2020 07:44 |
| Last Modified: | 07 Apr 2020 07:44 |
| URI: | https://pred.uni-regensburg.de/id/eprint/25856 |
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