Organobismuth(III) and organobismuth(V) complexes containing pyridyl and amino functional groups. Syntheses and characterizations of Bi(III)Ar-3 (Ar=p-C6H4(NMe2), p-C6H4CH2(NPr(i)(2)), p-C6H4[CH2N(2-Py)(2)]), Bi(V)Ar3L2, [Bi(V)Ar3Cl](2)O, [Bi(V)Ar-4][PF6], and [Bi(V)Ar-4](2)[Ag2Cl4] (Ar=p-C6H4(NMe2) or p-C6H4[CH2N(2-Py)(2)], L=Cl, CH3CO2(-), CF3CO2(-))

The synthesis of tertiary bismuth(III) complexes containing amino or pyridyl functional groups has been investigated. An improved synthesis for Bi[p-C6H4(NMe(2))](3) (1) has been achieved. Two new complexes, Bi[p-C5H4CH2(NPr2i)](3) (2) and Bi[p-C5H4CH2N(2-Py)(2)](3) (3), have been obtained. The bismuth(V) derivatives of compounds 1 and 3 have been synthesized via chlorine oxidation of 1 and 3 and the subsequent substitution reactions. Compounds Bi[p-C5H4(NMe(2))](3)(O2CCF3)(2) (5) and Bi{p-C5H4[CH2N(2-Py(2))]}(3)(O2CCH3)(2) (7) were obtained from the reactions of the corresponding dichloride complexes, BiAr3Cl2, with the appropriate silver salt. NMR spectroscopic studies established that in solution, compound 5 is fluxional while compound 7 is rigid. A dinuclear complex Bi-2[p-C6H4(NMe(2))]Cl-6(2)(O) (6) was isolated as the major product when the dichloride complex Bi[p-C6H4(NMe(2))]Cl-3(2) was reacted with NaOH in nondistilled reagent grade dichloromethane. A quaternary bismuth(V) complex, Bi[p-C6H4(NMe(2))](4)[PF6] (8), was obtained in good yield when Bi[p-C6H4(NMe(2))]Cl-3(2) was reacted with TlPF6 in a 1:2 ratio. A closely related quaternary bismuth(V) complex {Bi[p-C6H4(NMe(2))](4)}(2)[Ag2Cl4] (9), which contains an unusual three-coordinate dinuclear anion Ag2Cl42-, was obtained as a trace product from the reactions of Bi[p-C5H4(NMe(2))]Cl-3(2) with silver salts. The crystal structures of compounds 1 and 5-9 were determined by single-crystal X-ray diffraction analyses.