The preparation and reactivity of arylbismuth(III) dicarboxylates and diarylbismuth(III) carboxylates

Abstract

The compounds R₂BiO₂CR' (R = Ph, p-MeC₆H₄, p-MeOC₆H₄, p-EtOC₆H₄ or C₆F₅; R' = Me or CF₃) and RBi(O₂CR')₂ (R = Me, Ph, p-MeC₆H₄, p-MeOC₆H_~ or p-EtOC₆H₄; R' = Me or CF₃) are formed on acidolysis of the corresponding triarylbismuthines in ether. The products were readily identified by ¹H n.m.r. spectroscopy, even in complex mixtures, because of the successive downfield shifts of the aromatic resonances as the number of aryl groups decreases. By contrast with triarylbismuth compounds,R_3-n Bi(O₂CR')_n (R = aryl; n = 1 or 2) complexes are readily hydrolysed, whereas MeBi(O₂CMe), is oxygen-sensitive but more stable to hydrolysis. The compounds undergo aryl redistribution reactions in dimethyl sulfoxide.