Widmann, Maximilian and Riesinger, Christoph and Timoshkin, Alexey Y. and Blank, Philip M. and Scheer, Manfred (2025) Nucleophilic Functionalization of a Cationic Pentaphosphole Complex-A Systematic Study of Reactivity. CHEMISTRY-A EUROPEAN JOURNAL, 31 (15): e202404494. ISSN 0947-6539, 1521-3765
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The systematic nucleophilic functionalization of the cationic pentaphosphole ligand complex [Cp*Fe(eta 4-P5Me)][OTf] (A) with group 16/17 nucleophiles is reported. This method represents a highly reliable and versatile strategy for the design of novel transition-metal complexes featuring twofold substituted end-deck cyclo-P5 ligands, bearing unprecedented hetero-element substituents. By the reaction of A with classical group 16 nucleophiles, complexes of the type [Cp*Fe(eta 4-P5MeE)] (E=OEt (1), OtBu (2), SPh (3), SePh (4)) are obtained. By transferring this protocol to group 17 nucleophiles, the highly sensitive complexes [Cp*FeP5(eta 4-P5MeX)] (X=F (5), Cl (6), Br (7), I (8)) could be isolated. All products show exclusively 1,1'-substitution at the cyclo-P5 ring. Interestingly, further studies on the reactivity of the halogenated species revealed their ability to undergo ring-opening reactions with cyclic ethers such as THF and ethylene oxide yielding [Cp*FeP5(eta 4-P5MeOC4H8X)] (X=Br (9), I (10)) or [Cp*FeP5(eta 4-P5MeOC2H4X)] (X=Br (11), I (12)), respectively. Furthermore, the use of acyclic ethers such as dimethoxyethane led to the formation of [Cp*FeP5(eta 4-P5MeOC2H4OCH3)] (13) mediated by C-O bond cleavage, followed by subsequent P-O bond formation, as further enlightened by DFT calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | NONCOORDINATING ANIONS; COVALENT RADII; P5X2+ X; MECHANISM; TETRAHYDROFURAN; POLYMERIZATION; PHOSPHORUS; FERROCENE; CHEMISTRY; PENTAPHOSPHAFERROCENE; iron; nucleophilic functionalization; main group chemistry; 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: | 07 May 2026 04:29 |
| Last Modified: | 07 May 2026 04:29 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66452 |
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