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

Abstract

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), 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 for purification. The structures of 1–5 were confirmed by single-crystal X-ray diffraction. Compounds 2 and 5 exhibit a polymorph different from that previously reported in the literature. While all of the Bi(V) compounds adopt a trans-axial trigonal-bipyramidal configuration with the carboxylates in axial positions, there is considerable variation in the coordination of the carboxylate that ranges from simple η1 to a mixture of mono- and bidentate chelating bonding modes.