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), 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.