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Sigma/pi Bonding Preferences of Solvated Alkali‐Metal Cations to Ditopic Arylmethyl Anions
Author(s) -
Rae Annabel,
Byrne Keelan M.,
Brown Scott A.,
Kennedy Alan R.,
Krämer Tobias,
Mulvey Robert E.,
Robertson Stuart D.
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202104260
Subject(s) - alkali metal , deprotonation , chemistry , ring (chemistry) , lithium (medication) , denticity , lithium atom , crystallography , aromaticity , tetrahydrofuran , aryl , metal , medicinal chemistry , inorganic chemistry , stereochemistry , ion , organic chemistry , molecule , solvent , crystal structure , medicine , alkyl , ionization , endocrinology
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 Me 6 TREN 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.