0000000000177688
AUTHOR
Denis Bubrin
Isostructural Potassium and Thallium Salts of Sterically Crowded Thio‐ and Selenophenols: A Structural and Computational Study
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 isomorpho…
Formation of novel T-shaped NNN ligands via rare-earth metal-mediated Si-H activation.
Reactions of silylamides [Ln{N(SiHMe2)2}3(thf)2] with sterically crowded terphenylamine DmpNH2 (Dmp = 2,6-Mes2C6H3 with Mes = 2,4,6-Me3C6H2) afforded via a template reaction the formation of a new tridentate ligand, and derived complexes of composition [LnN{SiMe2N(Dmp)}2] (Ln = Ce, Pr) were obtained. Usage of the even more bulky amine Ar*NH2 (Ar* = 2,6-Trip2C6H3 with Trip = 2,4,6-iPr3C6H2) yielded the free protonated ligand NH{SiMe2NH(Ar*)}2.
2-Organoselenomethyl-1H-benzimidazole Complexes of Copper(II) and Copper(I)
Structurally characterized 2-methylselenomethyl-1H-benzimidazole (msbi) is shown to form complexes in 2:1 ratio with copper(II). Whereas the central cation [Cu(msbi)2Cl]+ = 1+ in [Cu(msbi)2Cl]Cl·2MeOH crystallizes in an approximately mixed square-pyramidal/trigonal-bipyramidal structure (τ = 0.52) with the second and third row atoms chlorine and selenium in the equatorial plane, the related [Cu(msbi)2(MeOH)](BF4)2 = [2](BF4)2 exhibits a closer to square-pyramidal arrangement with τ = 0.36 for that complex dication 22+. In both cases, the Cu–N bonds are short at about 1.94 A, whereas the Cu–Se distances vary between 2.62 A for 1+ and ca. 2.54 A for 22+. Slight differences between the Jahn–Te…