Garbagnati, Anna and Seidl, Michael and Balazs, Gabor and Scheer, Manfred (2022) Halogenation of the Hexaphosphabenzene Complex [(Cp*Mo)(2)(mu,eta(6):eta(6)-P-6)]: Snapshots on the Reaction Progress. CHEMISTRY-A EUROPEAN JOURNAL, 28 (32): e202200669. ISSN 0947-6539, 1521-3765
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The oxidation of [(Cp*Mo)(2)(mu,eta(6):eta(6)-P-6)] (1) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu,eta(1):eta(1):eta(1):eta(1)-P3I3)][X] (X=I-3(-), I-) (2) and [(Cp*Mo)(2)(mu,eta(4):eta(4)-P-4)(mu-PI2)][I-3] (3), while the reaction with PBr5 led to the complexes [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu-Br)(2)][Cp*MoBr4] (4) [(Cp*MoBr)(2)(mu,eta(3):eta(3)-P-3)(mu,eta(1)-P2Br3)] (5) and [(Cp*Mo)(2)(mu-PBr2)(mu-PHBr)(mu-Br)(2)] (6). The reaction of 1 with the far stronger oxidizing agent PCl5 was followed via time- and temperature-dependent P-31{H-1} NMR spectroscopy. One of the first intermediates detected at 193 K was [(Cp*Mo)(2)(mu,eta(3):eta(3)-P-3)(mu-PCl2)(2)][PCl6] (8) which rearranges upon warming to [(Cp*Mo)(2)(mu-PCl2)(2)(mu-Cl)(2)] (9), [(Cp*MoCl)(2)(mu,eta(3):eta(3)-P-3)(mu-PCl2)] (10) and [(Cp*Mo)(2)(mu,eta(4):eta(4)-P-4)(mu-PCl2)][Cp*MoCl4] (11), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ELECTRON LOCALIZATION; PHOSPHORUS; CHEMISTRY; TRANSFORMATION; ELEMENTS; BR; CP; bromine; chlorine; halogenation; hexaphosphabenzene; iodine; 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: | 14 Nov 2023 08:15 |
| Last Modified: | 14 Nov 2023 08:15 |
| URI: | https://pred.uni-regensburg.de/id/eprint/56647 |
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