Reactivity of Xantphos-Type Rhodium Complexes Towards SF₄: SF₃ Versus SF₂ Complex Generation

S-F-bond activation of sulfur tetrafluoride at [Rh(Cl)((tBu)xanPOP)] (1; (tBu)xanPOP=9,9-dimethyl-4,5-bis-(di-tert-butylphosphino)-xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF2)((tBu)xanPOP)][SF5] (2 a) together with trans-[Rh(Cl)(F)(2)((tBu)xanPOP)] (3) and cis-[Rh(Cl)(2)(F)((tBu)xanPOP)] (4) which both could also be obtained by the reaction of SF5Cl with 1. In contrast to that, the conversion of SF4 at the methyl complex [Rh(Me)((tBu)xanPOP)] (5) gave the isolable and room-temperature stable cationic lambda(4)-trifluorosulfanyl complex [Rh(Me)(SF3)((tBu)xanPOP)][SF5] (6). Treatment of 6 with the Lewis acids BF3 or AsF5 produced the dicationic difluorosulfanyl complex [Rh(Me)(SF2)((tBu)xanPOP)][BF4](2) (8 a) or [Rh(Me)(SF2)((tBu)xanPOP)][AsF6](2) (8 b), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF3)((tBu)xanPOP)][BF4] (9). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF2)((tBu)xanPOP)][Cl] (2 b) together with chloromethane and SF5Cl.