| Autor: |
Sanderson HJ; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K., Kociok-Köhn G; Material and Chemical Characterisation Facility, University of Bath, Claverton Down, Bath BA2 7AY, U.K., Hintermair U; Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.; Institute for Sustainability, University of Bath, Claverton Down, Bath BA2 7AY, U.K. |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2023 Oct 02; Vol. 62 (39), pp. 15983-15991. Date of Electronic Publication: 2023 Sep 15. |
| DOI: |
10.1021/acs.inorgchem.3c02087 |
| Abstrakt: |
The first magnesium pentalenide complexes have been synthesized via deprotonative metalation of 1,3,4,6-tetraphenyldihydropentalene ( Ph 4 PnH 2 ) with magnesium alkyls. Both the nature of the metalating agent and the reaction solvent influenced the structure of the resulting complexes, and an equilibrium between Mg[Ph 4 Pn] and [ n BuMg] 2 [Ph 4 Pn] was found to exist and investigated by NMR, XRD, and UV-vis spectroscopic techniques. Studies on the reactivity of Mg[Ph 4 Pn] with water, methyl iodide, and trimethylsilylchloride revealed that the [Ph 4 Pn] 2 - unit undergoes electrophilic addition at 1,5-positions instead of 1,4-positions known for the unsubstituted pentalenide, Pn 2 - , highlighting the electronic influence of the four aryl substituents on the pentalenide core. The ratio of syn / anti addition was found to be dependent on the size of the incoming electrophile, with methylation yielding a 60:40 mixture, while silylation yielded exclusively the anti -isomer. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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