Synthesis and Structure of Bismuth Complexes [(2-MeO)(5-Cl)C6H3]3Bi, [(2-MeO)(5-Cl)C6H3]3Bi[OC(O)CF2Br]2, and [(2-MeO)(5-Br)C6H3]3Bi[OC(O)C6HF4-2,3,4,5]2

In the crystal of [(2-MeO)(5-Cl)C6H3](3)Bi (I), obtained from bismuth trichloride and 2-methoxy-5-chlorophenyllithium in ether, bismuth atoms have a trigonal ligand environment. The coordination number of the central atom is 6 (3 + 3), with allowance made for the coordination of the MeO oxygen atom to the metal (the Bi center dot center dot center dot OMe intramolecular distances are 3.014(6), 3.088(6), and 3.168(6) angstrom). Treatment of a mixture of I and bromodifluoroacetic acid, or [(2-MeO)(5-Br)C6H3](3)Bi and 2,3,4,5-tetrafluorobenzoic acid in ether with tert-butyl hydroperoxide results in the formation of trigonal bipyramidal triarylbismuth dicarboxylates [(2-MeO)(5-Cl)C6H3](3)Bi[OC(O)CF2Br](2) (II) and [(2-MeO)(5-Br)C6H3](3)Bi[OC(O)C6HF4-2,3,4,5](2) (III), respectively, with carboxyl ligands in the apical positions. In the crystals of II and III, the metal atom is additionally coordinated to the oxygen atoms of the O=C and MeO groups (3.05(16), 3.30(16), and 3.153(5)-3.117(5) angstrom for II and 3.004(7), 3.230(7), and 3.159(7)-3.199(7) angstrom for III). The structures of I-III were studied by X-ray diffraction (CIF file CCDC nos. 2044006 (I), 2044005 (II), and 2048153 (III)).