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)( t Bu xanPOP)] ( 1 ; t Bu xanPOP=9,9‐dimethyl‐4,5‐bis‐(di‐tert‐butylphosphino)‐xanthene) led to the formation of the cationic complex [Rh(F)(Cl)(SF 2 )( t Bu xanPOP)][SF 5 ] ( 2 a ) together with trans‐ [Rh(Cl)(F) 2 ( t Bu xanPOP)] ( 3 ) and cis‐ [Rh(Cl) 2 (F)( t Bu 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)( t Bu xanPOP)] ( 5 ) gave the isolable and room‐temperature stable cationic λ 4 ‐trifluorosulfanyl complex [Rh(Me)(SF 3 )( t Bu 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 )( t Bu xanPOP)][BF 4 ] 2 ( 8 a ) or [Rh(Me)(SF 2 )( t Bu xanPOP)][AsF 6 ] 2 ( 8 b ), respectively. Refluorination of 8 a was possible with the use of dimethylamine giving [Rh(Me)(SF 3 )( t Bu xanPOP)][BF 4 ] ( 9 ). A reaction of 6 with trichloroisocyanuric acid (TClCA) gave the fluorido complex [Rh(F)(Cl)(SF 2 )( t Bu xanPOP)][Cl] ( 2 b ) together with chloromethane and SF 5 Cl.