Zimmermann, Lisa and Szlosek, Robert and Gassiot, Alexander Groer and Dütsch, Luis and Riesinger, Christoph and Scheer, Manfred (2025) Reactivity of a diphosphorus complex towards phosphenium ions. INORGANIC CHEMISTRY FRONTIERS, 12 (23). pp. 7813-7819. ISSN 2052-1553,
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The reaction of white phosphorus (P4) with phosphenium ions [R2P]+ yields [P5R2]+ cages via insertion of [R2P]+ into a P-P bond of P4. Herein, a systematic study on the reactivity of the P4 isolobal diphosphorus complex [{CpMo(CO)2}2(mu,eta 2:2-P2)] (A) towards differently substituted phosphenium ions was conducted. The phosphenium ions [R1R2P]+ (R1 = R2 = Cl, Br and R1 = Ph, R2 = Cl) were found to insert into a Mo-P bond of A followed by an unprecedented halide shift to yield [{CpMo(CO)2}2(mu,eta 1:1:1:1-P(R1)P(R2)P)][WCA] (1a: R1 = R2 = Cl, [WCA]- = [BArF24]-; 1b: R1 = R2 = Br, [WCA]- = [BArF24]-; 2: R1 = Ph, R2 = Cl, [WCA]- = [TEF]- with [BArF24]- = [B(3,5-C6H3(CF3)2)4]- and [TEF]- = [Al{OC(CF3)3}4]-). In contrast, [Ph2P]+ reacts with A in a complex reaction involving Mo-P and Mo-Mo bond insertion of the phosphenium ion leading to a mixture of [{CpMo(CO)}2(mu 4,eta 2:2:2:1:1-2-(Ph2P)P4)(mu-PPh2){CpMo(CO)2}2][TEF]2 (3) and [{CpMo(CO)}2(mu,eta 2:1:1-PP(Cl)PPh2)(mu-PPh2)][TEF] (4) depending on the used stoichiometry. Furthermore, the reaction of A with [Cy2P]+ leads to CO elimination and formation of [{CpMo(CO)}2(mu,eta 2:2-P2)(mu-PCy2)][TEF] (5) in which the phosphenium ion bridges the Mo-Mo bond. Reaction monitoring and additional DFT computations shed light on the ongoing reaction pathways and reveal crucial intermediates of the respective reactions.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | 2-COORDINATE PHOSPHORUS CATIONS; P-P BOND; COVALENT RADII; CHEMISTRY; SINGLE; P-4; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 16 Jun 2026 09:02 |
| Last Modified: | 16 Jun 2026 09:02 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66178 |
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