Abstract：
The 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.
摘要：
κ2-(P，N）-膦配体前体NH（CH2CH2PCy2）2可用于合成铑（I）配合物[Rh（CO）{3-（P，N,P)-Cy2PC2H4NHC2H4PCy2}][Cl](1)。去质子化络合物[Rh(CO){3-(P，N,P）-Cy2PC2H4NC2H4PCy2}]（2）在SO2F2的活化反应中显示PNP配体的协同反应性，以产生铑氟配合物反式-[Rh（F）（CO）{2-（P，P)-Cy2PC2H4N(SO2F)C2H4PCy2}]2(3)被S-F键裂解。值得注意的是，当用氢源例如二氢处理3时，没有观察到反应，有机硅化合物如三乙基硅烷或TMS-CF3和不同的氟源如SF4或Selectfluor®。然而,在CsF存在下用XeF2处理络合物3导致形成独特的氟化铑（III）络合物顺式，trans-[Rh(F)3(CO){2-(P，P)-Cy2PC2H4N(SO2F)C2H4PCy2}]2(4)。在吡啶（HFX）或BF3的存在下，氟配合物3转化为双阳离子配合物[Rh（CO）{2-（P，P)-Cy2PC2H4N(SO2F)-C2H4PCy2}]2[XF]2,X=HF(5)或BF3(6),分别。
