Reactivity of Xantphos‐Type Rhodium Complexes Towards SF(4): SF(3) Versus SF(2) 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)(SF(2))(( tBu)xanPOP)][SF(5)] (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 SF(5)Cl with 1. In contrast to that, the conversion of SF(4) at the methyl complex [Rh(Me)(( tBu)xanPOP)] (5) gave the isolable and room‐temperature stable cationic λ(4)‐trifluorosulfanyl complex [Rh(Me)(SF(3))(( tBu)xanPOP)][SF(5)] (6). Treatment of 6 with the Lewis acids BF(3) or AsF(5) produced the dicationic difluorosulfanyl complex [Rh(Me)(SF(2))(( tBu)xanPOP)][BF(4)](2) (8 a) or [Rh(Me)(SF(2))(( tBu)xanPOP)][AsF(6)](2) (8 b), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF(3))(( tBu)xanPOP)][BF(4)] (9). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF(2))(( tBu)xanPOP)][Cl] (2 b) together with chloromethane and SF(5)Cl.