REACTION OF [TI(CP)2(ASF6)2] (CP = ETA-C5H5) TOWARD S4N4 AND SE4N4 - IDENTIFICATION IN SOLUTION OF [TI(CP)2(S4N4)][ASF6]2 - SYNTHESIS AND CHARACTERIZATION OF [TI(CP)2F(ASF6)], [TI(CP)2F2]-ASF3 AND [TI(CP)F3]-ASF3

The reaction of [Ti(cp)2(AsF6)2] 2 (cp = eta-C5H5) with S4N4 in liquid sulphur dioxide gives [Ti(cp)2F(AsF6)] 4 and S4N4.AsF5 5. The new complex 4 can be prepared in quantitative yield from [Ti(cp)2F2] 1 and AsF5. Proton, N-14 and F-19 NMR spectroscopy reveals that SO2 solutions of 2 and S4N4 or 4 and 5 contain [Ti(cp)2(S4N4)][AsF6]2 3. In contrast Se4N4 is oxidized by 2 and leads to [(SeNSeNSe)2][AsF6]2, N2, AsF3 and 1. Complex 1 forms a stable adduct with AsF3, [Ti(cp)2F2].AsF3, which was characterized by H-1 NMR, IR and mass spectroscopy and elemental analysis. The monocyclopentadienyl analogue [Ti(cp)F3].AsF3 can also be prepared in quantitative yield from [Ti(cp)Cl3] and Ag[AsF6].