Understanding and tuning the electronic structure of pentalenides.
| Autor: | Jenek NA; Department of Chemistry, University of Bath Claverton Down Bath BA2 7AY UK u.hintermair@bath.ac.uk., Helbig A; Institute of Inorganic Chemistry, Institute for Sustainable Chemistry & Catalysis with Boron (ICB), Julius-Maximilians-Universität Würzburg Am Hubland D-97074 Würzburg Germany holger.helten@uni-wuerzburg.de., Boyt SM; Department of Chemistry, University of Bath Claverton Down Bath BA2 7AY UK u.hintermair@bath.ac.uk., Kaur M; Department of Chemistry, University of Bath Claverton Down Bath BA2 7AY UK u.hintermair@bath.ac.uk., Sanderson HJ; Department of Chemistry, University of Bath Claverton Down Bath BA2 7AY UK u.hintermair@bath.ac.uk., Reeksting SB; Chemical Characterisation Facility, University of Bath Claverton Down Bath BA2 7AY UK., Kociok-Köhn G; Chemical Characterisation Facility, University of Bath Claverton Down Bath BA2 7AY UK., Helten H; Institute of Inorganic Chemistry, Institute for Sustainable Chemistry & Catalysis with Boron (ICB), Julius-Maximilians-Universität Würzburg Am Hubland D-97074 Würzburg Germany holger.helten@uni-wuerzburg.de., Hintermair U; Department of Chemistry, University of Bath Claverton Down Bath BA2 7AY UK u.hintermair@bath.ac.uk. |
|---|---|
| Jazyk: | angličtina |
| Zdroj: | Chemical science [Chem Sci] 2024 Jul 05; Vol. 15 (32), pp. 12765-12779. Date of Electronic Publication: 2024 Jul 05 (Print Publication: 2024). |
| DOI: | 10.1039/d3sc04622b |
| Abstrakt: | Here we report the first example of systematic tuning of the electronic properties of dianionic pentalenides through a straightforward synthetic protocol which allows the controlled variation of substituents in the 1,3,4,6-positions to produce nine new compounds, representing the largest pentalenide study to date. Both electron-withdrawing as well as electron-donating aromatics have been incorporated to achieve different polarisations of the bicyclic 10π aromatic core as indicated by characteristic 1 H and 13 C NMR shifts and evaluated by DFT calculations including nucleus-independent chemical shift (NICS) scans, anisotropy of the induced current density (ACID) calculations, and natural bond orbital (NBO) charge distribution analysis. The introduction of methyl substituents to the pentalenide core required positional control in the dihydropentalene precursor to avoid exocyclic deprotonation during the metalation. Frontier orbital analyses showed arylated pentalenides to be slightly weaker donors but much better acceptor ligands than unsubstituted pentalenide. The coordination chemistry potential of our new ligands has been exemplified by the straightforward synthesis of a polarised anti -dirhodium(i) complex. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.) |
| Databáze: | MEDLINE |
| Externí odkaz: |
|