Intramolecular nucleophilic substitution in C6F5 moiety. The fluoride–dialkylamino exchange in decafluorodiphenlamino moiety

The reactions of [In(NEt2)3]2 and Sb(NEt2)3 with an equimolar amount of decafluorodiphenylamine (DFDPA, LH) lead to the indium or antimony amides [(C6F5)2NIn(NEt2)2]2 (1) and (C6F5)2NSb(NEt2)2 (2). Compound 2 rearranged further to give monofluoride Et2NSb(F)[N(o-Et2N–C6F4)(C6F5)] (3) and then difluoride F2Sb[N(o-Et2N–C6F4)2] (4). The hydrolysis of 4 gave free ligand HN(o-Et2N–C6F4)2 (5). Closely related HN(o-Me2N–C6F4)2 (6) was prepared from the reaction of Bi(NMe2)3 with DFDPA. The reactions of LiN(C6F5)2·THF with metal halides gave Sb[N(C6F5)2]3 (7), Me3Sb(Br)[N(C6F5)2] (8), Me3Sb(Cl)[N(C6F5)2] (9), Me3Sb[N(C6F5)2]2 (10), [Li(THF)2][In{N(C6F5)2}3Cl] (11). The X-ray structural investigations of 2 and 8 are presented.

The aminolysis of [In(NEt2)3]2, Sb(NEt2)3 and Bi(NMe2)3 with decafluordiphenylamine was studied. Bi(III) and Sb(III) alkylamides show an interesting ortho-directed C–F activation which was not observed in Sb(V) and In(III) compounds: [(C6F5)2NIn(NEt2)2]2 is stable whereas (C6F5)2NSb(NEt2)2 rearranges to give F2Sb[N(o-Et2N–C6F4)2]. Metathesis of halides with Li(THF)[N(C6F5)2] gave Sb[N(C6F5)2]3, Me3Sb(Br)N(C6F5)2, Me3Sb(Cl)N(C6F5)2, Me3Sb[N(C6F5)2]2, and Li(THF)2[In{N(C6F5)2}3Cl].Figure optionsDownload as PowerPoint slide