Intramolecular nucleophilic substitution in a C6F5 moiety assisted by antimonyстатья
Статья опубликована в высокорейтинговом журнале
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Аннотация:Antimony tris-amides-(Et2N)(3-n)Sb[N(C6F5)(2-C5H4N)](n) [n = 1 (3), 2 (4) or 3 (5)]-have been prepared by treatment of Sb(NEt2)(3) (1) with stoichiometric amounts of (2-C5H4N)(C6F5)NH (2). In contrast to amide 5, compounds 3 and 4 are unexpectedly unstable and react further to give the bis-amido antimony fluorides [(2-Et2N-C6F4)(2-C5H4N)N]Sb(F)[N(C2H5)(2)] (6) and [(2-Et2N-C6F4)(2-C5H4N)N]Sb(F)[N(C6F5)(2-C5H4N)] (7). The structure of 7 was confirmed by X-ray diffraction studies. DFT calculations, which reproduce the principal features of compound 7's geometry, have been used to explain the possible reaction pathway of this ortho-directed metathetical fluoride-amide exchange. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.