First solution-phase synthesis of bismuth(II) carboxylate

INOR 314

Margaret Napier, Alexander S. Filatov, af1869@albany.edu, Evgeny V. Dikarev, dikarev@albany.edu, and Marina A. Petrukhina, marina@albany.edu. Department of Chemistry, University at Albany, Albany, NY 12222
Bismuth trifluoroacetate, the first inorganic salt of bismuth in the oxidation state +2, was recently synthesized using a gas-phase comproportionation reaction of Bi(III) trifluoroacetate and bismuth metal. Later the solventless synthesis of heterobimetallic carboxylates, such as Bi(II)-Rh(II) and Bi(II)-Ru(II), has been developed. Although gas-phase reactions have several advantages, they are not suitable for a wide range of Bi(II) carboxylates and solution approaches are still needed. Herein, we report the first successful synthesis of Bi(II) trifluoroacetate from Bi(III) trifluoroacetate using solution-phase methods only. We found that the reduction can be carried out in a number of aromatic solvents but an addition of copious amounts of diphenyl ether is crucial for the reaction to proceed. The target product was obtained in a form of diphenyl ether adduct and was characterized by IR, NMR, and single crystal X-ray diffraction. Attempts toward evaluating the mechanism of the reaction are underway and will also be discussed.