Facile One-Pot Synthesis of Triphenylbismuth(V) Bis(carboxylate) Complexes

Triphenylbismuth(V) bis(carboxylates), Ph3Bi(O2CR)2 (R = 5-Br-2-OH-C6H3- (1), 2-OH-C6H4-(2), 2,6-(OH)2-C6H3- (3); 3-Me-2-NH2-C6H3- (4); Ph- (5) and Me- (6)) were obtained from the reaction of triphenylbismuth with hydrogen peroxide and excess carboxylic acid in wet 2-propanol. The synthesis avoids the use of halogens as oxidants and the products crystallize directly from the solution as pure compounds. They crystallize from solution without further need of purification. The structures of 1 - 5 were confirmed by single crystal X-ray diffraction. Compounds 2 and 5 exhibit a different polymorph than that previously reported in the literature. While all of the Bi(V) compounds adopt a trans-axial trigonal-bipyramidal configuration with the carboxylates in the axial positions, there is considerable variation in the coordination of the carboxylate that ranges from simple monohapto to the mixture of mono- and bidentate chelating bonding modes