Riesinger, Christoph and Dielmann, Fabian and Szlosek, Robert and Virovets, Alexander V. and Scheer, Manfred (2023) Synthesis and Reactivity of a Cyclooctatetraene-Like Polyphosphorus Ligand Complex [Cyclo-P8]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 62 (16). ISSN 1433-7851, 1521-3773
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The thermolysis of Cp ''' Ta(CO)(4) with white phosphorus (P-4) gives access to [{Cp ''' Ta}(2)(mu,eta(2 : 2 : 2 : 2 : 1 : 1)-P-8)] (A), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P-8 ligand. While ring sizes of n >6 have remained elusive for cyclo-P-n structural motifs, the choice of the transition metal, co-ligand and reaction conditions allowed the isolation of A. Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp ''' Ta}(4)(mu(4),eta(2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1)-P-16)][TEF](2) (4, TEF=[Al(OC{CF3}(3))(4)](-)). Reduction, however, leads to the fission of one P-P bond in A followed by rapid dimerization to form [K@[2.2.2]cryptand](2)[{Cp ''' Ta}(4)(mu(4),eta(2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1)-P-16)] (5), which features an unprecedented chain-type P-16 ligand. Lastly, A serves as a P-2 synthon, via ring contraction to the triple-decker complex [{Cp ''' Ta}(2)(mu,eta(6 : 6)-P-6)] (B).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | METAL-MEDIATED ACTIVATION; P-4 ACTIVATION; CHEMISTRY; PHOSPHORUS; PENTAPHOSPHAFERROCENE; COORDINATION; DIPHOSPHORUS; AGGREGATION; INSERTION; CHAIN; Cyclo-P-8; DFT Calculations; Phosphorus; Polyphosphorus; Tantalum |
| 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: | 12 Mar 2024 13:55 |
| Last Modified: | 12 Mar 2024 13:55 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59783 |
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