Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 15983-15991 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 62 |
| Issue number | 39 |
| Early online date | 15 Sept 2023 |
| DOIs | |
| Publication status | Published - 2 Oct 2023 |
Bibliographical note
The authors thank the Royal Society (award UF160458) and the University of Bath for funding this work. Dr Mandeep Kaur is acknowledged for help with the synthesis and isolation of several compounds, Dr Kathryn Proctor for assistance with mass spectrometry measurements, and Prof. Mike Hill for fruitful discussions and advice on Mg chemistry.Funding
The authors thank the Royal Society (award UF160458) and the University of Bath for funding this work. Dr Mandeep Kaur is acknowledged for help with the synthesis and isolation of several compounds, Dr Kathryn Proctor for assistance with mass spectrometry measurements, and Prof. Mike Hill for fruitful discussions and advice on Mg chemistry. ⊥