The Unexpected Isolation of Bismuth Tris(carboxylate) Hydrates: Syntheses and Structures of [Bi(Hsal)3(H2O)] and [Bi(Hanth)3(H2O)] (H2sal = 2-OH-C6H4CO2H, Hanth = 2-NH2-C6H4CO2H)
Whitmire, Kenton H.
A complex of the composition [Bi(2-OH-C6H4CO2)3(H2O)] (1) was isolated from the 1:3 reaction of BiPh3 with H2sal (H2sal = salicylic acid = 2-OH-C6H4CO2H) in wet xylene, and the analogous anthranilate compound [Bi(2-NH2-C6H4CO2)3(H2O)] (2) was obtained from the 1:3 reaction of Bi(OtBu)3 with Hanth (Hanth = anthranilic acid = 2-NH2-C6H4CO2H) in tetrahydrofuran. Compounds 1 and 2 were fully characterized spectroscopically and by single-crystal X-ray diffraction. Compounds 1 and 2 crystallize in the triclinic space group and display the η2-(O,O′) binding mode for the oxygen atoms of the carboxylate ligands. There are two independent molecules in the asymmetric units of 1 and 2 that are connected by a weak bridging interaction of the OH or NH2 group to an adjacent molecule. Both bismuth atoms are bound to a H2O molecule, but the distances are highly asymmetric, long Bi···O lengths ranging from 2.74 to 2.89 Å.
bismuth; salicylates; carb-oxylates; hydrates; hydrolysis