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

Sodium tetraarylborate salts NaBAr 4 (Ar = C 6 H 5 (Ph), C 6 H 4 -Me-4 (tolyl), C 6 H 4 -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-C 6 H 4 CO 2 − (Hsal); 4-Me-2-HO-C 6 H 3 CO 2 − (Hsal 4Me ); or 3-MeO-2-HO-C 6 H 3 CO 2 − (Hsal 3OMe )) and Bi(O 2 CR) 3 (R = Me, CMe 3, and CF 3 ) 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 BiPh x (tolyl) 3− x . Formation of the known arylbismuth compounds was confirmed by IR spectroscopy, X-ray crystallography, NMR spectroscopy ( 1 H, 11 B, 13 C, and 19 F), 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.