Anion exchange of BF(4)(-) occurs by stirring a cobalt(III) complex of salen-type ligand tethered by four quaternary ammonium BF(4)(-) salts over a slurry of NaX in CH(2)Cl(2), affording a complex containing four X's per cobalt (X = 2,4,5-trichlorophenolate, 6; X = 4-nitrophenolate, 10; X = 2,4-dichlorophenolate, 12). The (1)H and (13)C NMR spectra are in agreement with an unusual imine uncoordinated structure. The two salen-phenoxys and the two X's persistently coordinate with cobalt(III) to form a square planar cobaltate complex while the other two X's scramble through coordination and decoordination to the axial sites of the square plane. Another form of the complex (X = 2,4,5-trichlorophenolate, 14; X = 4-nitrophenolate, 15; X = 2,4-dichlorophenolate, 16) is also prepared, in which the scrambling two X's in 6, 10, or 12 are replaced with the corresponding [X...H...X](-) homoconjugate. These complexes, which adopt an unusual imine uncoordinated structure, are excellent catalysts for CO(2)/propylene oxide copolymerization (turnover frequency (TOF), 8300-16,000 h(-1)). In all cases, the complex containing the homoconjugate [X...H...X](-) shows higher activity than the corresponding phenol-free complex. Among the prepared complexes, 4-nitrophenol-4-nitrophenolate homoconjugate complex 15 showed the best performance (TOF, 16,000 h(-1); selectivity, 98%; M(n), 273,000), allowing for replacement of the explosive 2,4-dinitrophenolate complex.
