A Synthetic, Structural, Spectroscopic, and Computational Study of Alkali Metal–Thioether, −Selenoether, and −Telluroether Interactions
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abstract
The rigid thioether- and selenoether-containing pro-ligands, 4,5-bis(phenylsulfido)-2,7,9,9-tetramethylacridan (H[AS2Ph2] (1)) and 4,5-bis(phenylselenido)-2,7,9,9-tetramethylacridan (H[ASe2Ph2] (2)), were deprotonated with one equiv of nBuLi to afford dimeric lithium complexes [Li(AE2Ph2)]2 (E = S (3), Se (4)) or with one equiv of KCH2Ph to afford the previously reported potassium complexes [K(AS2Ph2)(dme)]x (5) and [K(ASe2Ph2)(dme)2] (6). Attempts to prepare a direct telluroether analogue of compounds 1-2 were unsuccessful. However, the bulky selenoether- and telluroether-containing pro-ligands 4,5-bis(2,4,6-triisopropylphenylselenido)-2,7,9,9-tetramethylacridan (H[ASe2Tripp2] (7)) and 4,5-bis(2,4,6-triisopropylphenyltellurido)-2,7,9,9-tetramethylacridan (H[ATe2Tripp2] (8)) were accessed via the reaction of 4,5-dibromo-2,7,9,9-tetramethylacridan with three equiv of nBuLi, followed by the addition of two equiv of the corresponding diaryl dichalcogenide and quenching with dilute HCl(aq). The new selenoether- and telluroether-containing pro-ligands were subsequently deprotonated using KCH2Ph to afford [K(AE2Tripp2)(dme)2] (E = Se (9), Te (10)). Compounds 1-10 were characterized by 1H, 13C{1H}, 77Se{1H}, 125Te{1H}, and 7Li NMR spectroscopy, where applicable, and single-crystal X-ray structures were obtained for all lithium and potassium complexes (3-6 and 9-10). DFT calculations were also performed to assess the nature of bonding between the hard group 1 cations and the soft chalcogenoethers.
