Zimmermann, Lisa and Riesinger, Christoph and Balazs, Gabor and Scheer, Manfred (2023) Synthesis and Reactivity of Hetero-Pnictogen Diazonium Analogs Stabilized by Transition Metal Units. CHEMISTRY-A EUROPEAN JOURNAL, 29 (61): e202301974. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The reactivity of the mixed dipnictogen complexes [{CpMo(CO)(2)}(2)(mu,eta(2:2)-PE)] (E= P, As, Sb) towards different group 14 electrophiles is reported. The resulting library of cationic compounds [{CpMo(CO)2}2(mu,eta(2:2)-EPR)]+ (R= Mes (2,4,6-C6H2Me3), CH3, CPh3, SnMe3) represents formally inorganic diazonium homologs which are stabilized by transition metal units. Modifying the steric and electronic properties of the electrophile drastically impacts the respective P R bond lengths and is accompanied by increasing (SnMe3> CPh3> CH3) dynamic behavior in solution. In contrast to the well-studied organic analogs, the prepared compounds are stable at room temperature. The subsequent reaction of the model substrate [{CpMo(CO)(2)}(2)(mu,eta(2:2)-P2Me)][OTf] ([OTf] =[CF3SO3]) with different N-heterocyclic carbenes (NHCs) leads to an addition at the unsubstituted P atom which is also predicted by computational methods. NMR spectroscopy confirms the formation of two isomers sync/gauche-[{CpMo(CO)(2)}(mu,eta(2:1)-P(NHC)PMe){CpMo(CO)(2)}][OTf]. X-ray crystallographic characterization and additional DFT calculations shed light on the spatial arrangement as well as on the possible formation pathways of the isomers.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COVALENT RADII; COORDINATION; DIPHOSPHORUS; PHOSPHORUS; COMPLEXES; TETRAFLUOROBORATE; PHOSPHAALKYNES; CHEMISTRY; VERSATILE; SINGLE; antimony; arsenic; diazonium salt; molybdenum; 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: | 05 Mar 2024 11:56 |
| Last Modified: | 05 Mar 2024 11:56 |
| URI: | https://pred.uni-regensburg.de/id/eprint/59305 |
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