Activation of SO2F2 at a Rhodium PNP Pincer Complex: Ligand Supported S−F Bond Cleavage to Generate NSO2F Derivatives

Abstract

AbstractThe κ2‐(P,N)−phosphine ligand precursor NH(CH2CH2PCy2)2 can be used for the synthesis of the rhodium(I) complex [Rh(CO){ĸ3‐(P,N,P)−Cy2PC2H4NHC2H4PCy2}][Cl] (1). The deprotonated complex [Rh(CO){ĸ3‐(P,N,P)−Cy2PC2H4NC2H4PCy2}] (2) shows a cooperative reactivity of the PNP ligand in the activation reaction of SO2F2 to yield the rhodium fluorido complex trans‐[Rh(F)(CO){ĸ2‐(P,P)−Cy2PC2H4N(SO2F)C2H4PCy2}]2 (3) by S−F bond cleavage. It is remarkable that no reaction was observed when 3 was treated with hydrogen sources e. g. dihydrogen, organosilicon compounds such as triethylsilane or TMS−CF3 and different fluorine sources such as SF4 or Selectfluor®. However, the treatment of complex 3 with XeF2 in the presence of CsF resulted in the formation of the unique fluorido rhodium(III) complex cis,trans‐[Rh(F)3(CO){ĸ2‐(P,P)−Cy2PC2H4N(SO2F)C2H4PCy2}]2 (4). In the presence of pyridine(HF)X or BF3 the fluorido complex 3 converted into the dicationic complexes [Rh(CO){ĸ2‐(P,P)−Cy2PC2H4N(SO2F)C2H4PCy2}]2[XF]2, X=HF (5) or BF3 (6), respectively.