A New Methodology for Synthesis of Aryl Bismuth Compounds: Arylation of Bismuth(III) Carboxylates by Sodium Tetraarylborate Salts

Sodium tetraarylborate salts Na[BAr4] (Ar = C6H5 (Ph), C6H4-Me-4 (tolyl), C6H4-F-4) are found to be efficient arylating species for a range of bismuth(III) aromatic and aliphatic carboxylates including Bi(Hsal*)3 (Hsal* = 2-HO-C6H4CO2− (Hsal); 4-Me-2-HO-C6H3CO2− (Hsal4Me); or 3-MeO-2-HO-C6H3CO2− (Hsal3OMe)) and Bi(O2CR)3 (R = Me, CMe3, and CF3) to produce triaryl bismuth compounds. The reactions may be carried out in ethanol, tetrahydrofuran, or acetone. The arylbismuth bis(salicylates) BiPh(Hsal)2 and Bi(tolyl)(Hsal)2 exhibit similar reactivity in refluxing THF and may be used to produce mixed arylbismuthines BiPhx(tolyl)3−x. Formation of the known arylbismuth compounds was confirmed by IR spectroscopy, X-ray crystallography, NMR spectroscopy (1H, 11B, 13C, and 19F), and mass spectrometry. This is a facile synthesis of both symmetrical and unsymmetrical triarylbismuthines involving the aryl group transfer from the tetraarylborate ions to bismuth(III) under mild conditions.