Widmann, Maximilian and Riesinger, Christoph and Szlosek, Robert and Balazs, Gabor and Scheer, Manfred (2024) Electrophilic Functionalization of a Hexaphosphabenzene Ligand in [(CpMo)2(μ,η<SUP>6: 6</SUP>-P6)]. CHEMISTRY-A EUROPEAN JOURNAL, 30 (19). ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The electrophilic functionalization of the triple-decker sandwich complex [{Cp*Mo}(2)(mu,eta(6:6)-P-6)] (A) and its mono-oxidized counterpart [{Cp*Mo}(2)(mu,eta(6:6)-P-6)][SbF6] (B) with reactive main-group electrophiles as well as radical scavengers is shown to be a reliable method for the selective functionalization of the hexaphosphabenzene ligand. Depending on the electrophile used, the regioselectivity of the functionalization can be adjusted. Using group 16 electrophiles, the trisubstituted compounds [{Cp*Mo}(2){(mu,eta(3 : 3)-P-3)(mu,eta(1 : 1 : 1 : 1)-1,3-(SePh)(2)-2-Br-P-3)}][TEF] (1), [{Cp*Mo}(2)(mu,eta(3 : 3)-P-3)(mu,eta(1 : 1 : 1 : 1)-1,2,3-(EPh)(3)-P-3)][SbF6] (E=S (2), Se (3)) as well as the side product [{Cp*Mo}(2)(mu,eta(4:4)-P-4)(mu,eta(1 : 1)-P(SPh)(2))][SbF6] (4) are obtained. By switching to phosphenium ions as group 15 electrophiles, the ring-inserted products [{Cp*Mo}(2)(mu,eta(3 : 3 : 2 : 2)-P7R2)][TEF] (R=Cy (5), Pr-i (6)) are isolated, showing an unprecedented P7R2 structural motif. Furthermore, the reaction with MeOTf yields the dimeric [{Cp*Mo}(4)(1,4-Me-2-mu(4),eta(1 : 1 : 1 : 1 : 1 : 1)-P-6)(mu,eta(3 : 3)-P-3)(2)][TEF](2) (7) as the first example of a complex featuring two interconnected cyclo-P-6 middle deck ligands. Finally, by combination of the methylation step with Ph2Se2, the mixed group 14/16 complex [{Cp*Mo}(2){(mu,eta(3 : 3)-P-3)(mu,eta(1 : 1 : 1 : 1)1,2-(SePh)(2)-3-Me-P-3)}][OTf] (8) is obtained.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | WEAKLY COORDINATING ANIONS; BOND COVALENT RADII; P-P BOND; P5X2+ X; ELEMENTS; PHOSPHORUS; DERIVATIVES; MOLECULES; CATIONS; COMPLEX; chalcogens; electrophilic substitution; molybdenum; phosphorus; triple decker complexes |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 25 Jul 2025 09:02 |
| Last Modified: | 25 Jul 2025 09:02 |
| URI: | https://pred.uni-regensburg.de/id/eprint/63776 |
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