Synthesis, Structure, and Reactivity of Magnesium Pentalenides

Hugh J Sanderson, Gabriele Kociok-Köhn, Ulrich Hintermair

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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 languageEnglish
Pages (from-to)15983-15991
Number of pages9
JournalInorganic Chemistry
Volume62
Issue number39
Early online date15 Sept 2023
DOIs
Publication statusPublished - 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.

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