Arylmethyl anions allow alkali‐metals to bind in a σ‐fashion to the lateral carbanionic centre or a π‐fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2‐benzylpyridine and 4‐benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me6TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X‐ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)−M interactions regardless of alkali‐metal, although the adjacent arene carbons engage in interactions with larger alkali‐metals. Introducing a nitrogen atom into the ring (at the 2‐ or 4‐position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2‐pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza‐allyl formation at the other extremity (potassium), while C‐ or N‐coordination modes become energetically viable for Na and K phenyl(4‐pyridyl)methyl complexes.
The benchmark magnesium electrolyte, [Mg2Cl3]+ [AlPh4]-, can be prepared in a 100% atom-economic fashion by a ligand exchange reaction between AlCl3 and two molar equivalents of MgPh2. NMR and vibrational...
We explore the suitability of operando attenuated total
reflection
infrared (ATR-IR) spectroscopy methodologies for the study of organoaluminate
electrolytes for Mg battery applications. The “all-phenyl complex”
in tetrahydrofuran (THF), with the molecular structure [Mg2Cl3·6THF]+[AlPh4]−, is used as an exemplar electrolyte to compare two different spectroelectrochemical
cell configurations. In one case, a Pt gauze is used as a working
electrode, while in the second case, a thin (∼10 nm) Pt film
working electrode is deposited directly on the surface of the ATR
crystal. Spectroscopic measurements indicate substantial differences
in the ATR-IR response for the two configurations, reflecting the
different spatial arrangements of the working electrode with respect
to the ATR sampling volume. The relative merits and potential pitfalls
associated with the two approaches are discussed.
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