From an Isolable Bismolyl Anion to an Yttrium-Bismolyl Complex with μ-Bridging Bismuth(I) Centers and Polar Covalent Y-Bi Bonds.

Abstract

The synthesis and first structural characterization of the [K(18-crown-6)] bismolyl Bitet (C4 Me4 Bi) contact ion pair (1) is presented. Notably, according to Natural Resonance Theory calculations, the Bitet anion of 1 features two types of leading mesomeric structures with localized anionic charge and two lone pairs of electrons at the BiI center, as well as delocalized anionic charge in the π-conjugated C4 Bi ring. The lone pairs at Bi enable a unique bridging coordination mode of the bismolyl ligand, as shown for the first rare earth metal bismolyl complex (Cptet 2 Y)2 (μ-η1 -Bitet )2 (2). The latter results from the salt metathesis reaction of KBitet with Cptet 2 Y(BPh4 ) (Cptet =C5 Me4 H). The Y-Bi bonding interaction in 2 of 16.6 % covalency at yttrium is remarkably large.