Riesinger, Christoph and Duetsch, Luis and Balazs, Gabor and Bodensteiner, Michael and Scheer, Manfred (2020) Cationic Functionalisation by Phosphenium Ion Insertion. CHEMISTRY-A EUROPEAN JOURNAL, 26 (71). pp. 17165-17170. ISSN 0947-6539, 1521-3765
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The reaction of [Cp ''' Ni(eta(3)-P-3)] (1) with in situ generated phosphenium ions [RR ' P](+) yields the unprecedented polyphosphorus cations of the type [Cp ''' Ni(eta(3)-P4R2)][X] (R=Ph (2 a), Mes (2 b), Cy (2 c), 2,2 '-biphen (2 d), Me (2 e); [X](-)=[OTf](-), [SbF6](-), [GaCl4](-), [BArF](-), [TEF](-)) and [Cp ''' Ni(eta(3)-P4RCl)][TEF] (R=Ph (2 f), tBu (2 g)). In the reaction of 1 with [Br2P](+), an analogous compound is observed only as an intermediate and the final product is an unexpected dinuclear complex [{Cp ''' Ni}(2)(mu,eta(3):eta(1):eta(1)-P4Br3)][TEF] (3 a). A similar product [{Cp ''' Ni}(2)(mu,eta(3):eta(1):eta(1)-P-4(2,2 '-biphen)Cl)][GaCl4] (3 b) is obtained, when 2 d[GaCl4] is kept in solution for prolonged times. Although the central structural motif of 2 a-g consists of a "butterfly-like" folded P-4 ring attached to a {Cp ''' Ni} fragment, the structures of 3 a and 3 b exhibit a unique asymmetrically substituted and distorted P-4 chain stabilised by two {Cp ''' Ni} fragments. Additional DFT calculations shed light on the reaction pathway for the formation of 2 a-2 g and the bonding situation in 3 a.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | P-P BOND; COORDINATION SPHERE; WHITE PHOSPHORUS; COVALENT RADII; P5X2+ X; COMPLEXES; CHEMISTRY; BR; POLYARSENIDES; REACTIVITY; nickel; phosphenium cations; phosphorus; polyphosphorus cations; ring expansion |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 08 Mar 2021 07:45 |
| Last Modified: | 08 Mar 2021 07:45 |
| URI: | https://pred.uni-regensburg.de/id/eprint/43337 |
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