ORGANOBISMUTH(III) AND ORGANOBISMUTH(V) COMPLEXES CONTAINING PYRIDYL AND AMINO FUNCTIONAL-GROUPS - SYNTHESES AND CHARACTERIZATIONS OF BI(III)AR-3 (AR=P-C6H4(NME(2)), P-C6H4CH2(NPR2I), P-C6H4[CH2N(2-PY)(2)]), BI(V)AR(3)L(2), [BI(V)AR3CL]O-2, [BI(V)AR-4][PF6], AND [BI(V)AR-4](2)[AG2CL4] (AR=P-C6H4(NME(2)) OR P-C6H4[CH2N(2-PY)(2)], L=CL, CH3CO2-, CF3CO2-)

The synthesis of tertiary bismuth(III) complexes containing amino or p yridyl 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 bee n obtained. The bismuth(V) derivatives of compounds 1 and 3 have been synthesized via chlorine oxidation of 1 and 3 and the subsequent subst itution 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 rea ctions of the corresponding dichloride complexes, BiAr3Cl2, with the a ppropriate silver salt. NMR spectroscopic studies established that in solution, compound 5 is fluxional while compound 7 is rigid. A dinucle ar complex Bi-2[p-C6H4(NMe(2))]Cl-6(2)(O) (6) was isolated as the majo r product when the dichloride complex Bi[p-C6H4(NMe(2))]Cl-3(2) was re acted with NaOH in nondistilled reagent grade dichloromethane. A quate rnary 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 i n a 1:2 ratio. A closely related quaternary bismuth(V) complex {Bi[p-C 6H4(NMe(2))](4)}(2)[Ag2Cl4] (9), which contains an unusual three-coord inate dinuclear anion Ag2Cl42-, was obtained as a trace product from t he reactions of Bi[p-C5H4(NMe(2))]Cl-3(2) with silver salts. The cryst al structures of compounds 1 and 5-9 were determined by single-crystal X-ray diffraction analyses.