Synthesis and structure of triphenylbismuth bis(fluorobenzoates)

摘要

The reaction between triphenylbismuth, hydrogen peroxide, and 3,4,5-trifluorobenzoic or pentafluorobenzoic acid (molar ratio 1:1:2, respectively) in ether gave triphenylbismuth bis(3,4,5-trifluorobenzoate) (I) and triphenylbismuth bis(pentafluorobenzoate) (II) in 74 and 89% yields, respectively. The structures of compounds I and II were established by X-ray diffraction. The Bi atoms have a distorted trigonal - bipyramidal coordination with acylate groups in the axial positions. The OBiO angles are 170.2(2) deg and 171.5(2) deg in I and II, respectively. The Bi-C(Ph)_(eq) bond lengths vary in the range of 2.187(6)-2.204(5) A, the Bi-O(acyl) lengths are 2.256(5) A in I, and 2.281(5) and 2.318(5) A in II. In the crystals I and II, the Bi and carbonyl O atoms are involved in intramolecular interactions (Bi…O(=C) 2.926(5)-3.176(5)A), which increase the equatorial CBiC angles on the side of these contacts to 136.2(3) deg and 138.6(2) deg in I and II, respectively.