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RESEARCH PRODUCT

Isostructural Potassium and Thallium Salts of Sterically Crowded Thio‐ and Selenophenols: A Structural and Computational Study

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Because of their similar cationic radii, potassium and thallium(I) compounds are usually regarded as closely related. Homologous molecular species containing either K+ or Tl+ are very rare, however. We have synthesized potassium and thallium salts MEAr* [M, E = K, S (2a); K, Se (2b); Tl, S (3a); Tl, Se (3b); Ar* = 2,6-Trip2C6H3, Trip = 2,4,6-iPr3C6H2] derived from terphenyl-substituted thio- and selenophenols. In the solid-state structures of dimeric 2a, 2b, 3a, and 3b additional metal-ηn–π-arene interactions to the flanking arms of the terphenyl substituents of different hapticity n are observed. Remarkably, the homologous potassium and thallium complexes 2b and 3b crystallize in isomorphous cells. For 2a, 3a, and model complexes of the composition METph (Tph = C6H4-2-Trip) the nature of the M–E and M···C(arene) bonding was studied by density functional theory calculations.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)