Riesinger, Christoph and Blank, Philip M. and Scholtes, Christian and Gschwind, Ruth M. and Scheer, Manfred (2024) Enhancing the Reactivity of an Aromatic cyclo-P5 Ligand via Electrophilic Activation. CHEMISTRY-A EUROPEAN JOURNAL, 30 (68). ISSN 0947-6539, 1521-3765
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Electrophilic activation of the aromatic cyclo-P5 ligand in [Cp*Fe(eta 5-P5)] is demonstrated to drastically enhance its reactivity towards weak nucleophiles. Unprecedented functionalized, contracted as well as complexly aggregated polyphosphorus compounds are accessed utilizing [Cp*Fe(eta 5-P5Me)][OTf] (A), highlighting the great potential of this underexplored mode of reactivity. Addition of carbenes to A affords novel 1,2- or 1,1-difunctionalized cyclo-P5 complexes [Cp*Fe(eta 4-P5(1-L)(2-Me)][OTf] (L=IDipp (1), EtCAAC (2), IiPr (3 b)) and [Cp*Fe(eta 4-P5(1-IiPr)(1-Me)][OTf] (3 a). For the first time, the much smaller IMe4 leads to the contraction of the cyclo-P5 ligand and formation of [Cp*Fe(eta 4-P4(1-IMe)(4-Me)] (4). DFT calculations shed light on the delicate mechanism of this type of reaction, which is reinforced by the experimental identification of key intermediates. Even the comparably weak nucleophile IDippCH2 reacts with A to form [Cp*Fe(eta 4-P5(1-IDippCH2)(1/2-Me)][OTf] (6 a/b), highlighting its explicitly more reactive nature. Moreover, exposure of A to IDippEH (E=N, P) leads to a unique aggregation reaction affording [{Cp*Fe}2{mu 2,eta 4:3:1-P10Me2(IDippN)}][OTf] (8) and [{Cp*Fe}2{mu 2,eta 4:1:1:1-P11Me2(IDipp)}][OTf] (9), respectively.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HYBRID DENSITY FUNCTIONALS; WHITE PHOSPHORUS; COORDINATION SPHERE; RING EXPANSION; COMPLEXES; P-4; CHEMISTRY; PENTAPHOSPHAFERROCENE; CATIONS; IRON; Aromaticity; Carbene; Cyclo-P5; Electrophilic activation; Phosphorus |
| 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: | 18 Nov 2025 13:21 |
| Last Modified: | 18 Nov 2025 13:21 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63794 |
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