Evidence for SO 2, C 2H 4Cl 2 and CH 2Cl 2 soluble salts of bismuth homopolyatomic cations and [Bi 4OF 2Cl 6(C 6Me 6) 4][Al(OC(CF 3) 3) 4] 2 · C 6Me 6, containing the novel [Bi 4OF 2Cl 6] 2+ cation

Abstract

Evidence is presented that the SO 2, C 2H 4Cl 2 and CH 2Cl 2 soluble salts of composition [Bi x ][Al(OC(CF 3) 3) 4] 3 ( 1), x close to 4.33, and [Bi 5(C 6Me 6) 4][Al(OC(CF 3) 3) 4] 3 ( 2), have been prepared in moderate yields by the metathesis reaction of [Bi 5][AsF 6] 3 and Li[Al(OC(CF 3) 3) 4] in SO 2, and in CH 2Cl 2 in the presence of C 6Me 6, respectively. The compositions of 1 and 2 are supported by elemental analysis, IR, NMR and EI-MS. The UV–Vis spectra of 1 and 2 in SO 2 and C 2H 4Cl 2 were consistent with the presence of the bismuth cations [Bi 5] 3+, [Bi 8] 2+, [Bi] + and possibly [Bi 9] 5+. The 1:2 salt [Bi 4OF 2Cl 6(C 6Me 6) 4][Al(OC(CF 3) 3) 4] 2 · C 6Me 6 ( 3 · C 6Me 6) was isolated from a solution of 2, and characterized by preliminary X-ray crystal structure, NMR and IR. Complex 3 contains a discrete oxygen-centered fluorine and chlorine-bridged bismuth cluster [Bi 4OF 2Cl 6] 2+ with each bismuth weakly coordinated to hexamethylbenzene.