Details

Autor(en) / Beteiligte

• Shutov, Pavel L.
• Karlov, Sergey S.
• Harms, Klaus
• Zabalov, Maxim V.
• Sundermeyer, Jörg
• Lorberth, Jörg
• Zaitseva, Galina S.

Titel

ortho-Directed Metathetical Fluoride/Amide Exchange in (Pentafluorophenyl)amides

Ist Teil von

• European Journal of Inorganic Chemistry, 2007-12, Vol.2007 (36), p.5684-5692

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2007

Quelle

Wiley Online Library All Journals

Beschreibungen/Notizen

• The indium tris(amide)s [(Et2N)3–nIn{N(C6F5)(2‐C5H4N)}n] [n = 1 (15), 2 (16) or 3 (9)] have been prepared by treatment of [In(NEt2)3]2 (3) with a stoichiometric amount of (2‐C5H4N)(C6F5)NH (1). The analogous reaction of Bi(NMe2)3 (2) with 3 equiv. of amine 1 and the treatment of BiCl3 (5) with a stoichiometric amount of (2‐C5H4N)(C6F5)NLi (4) both lead to [Bi{N(C6F5)(2‐C5H4N)}3] (10). In contrast, only the difluoride 11 or the monofluoride 12, which are the products of intramolecular ortho‐directed exchange of NMe2 and F substituents, are obtained from the reaction of 2 with 1 or 2 equiv. of 1, respectively. The reaction between Me3Sb(Hal)2 [Hal = Br (7) Cl, (8)] and 1 or 2 equiv. of lithium salt 4 gives the corresponding stable monoamides [Me3(Hal)Sb{N(C6F5)(2‐C5H4N)}] [Hal = Br (17), Cl (18)] or bis(amide) [Me3Sb{N(C6F5)(2‐C5H4N)}2] (19), respectively. The structure of 9 has been confirmed by an X‐ray structure analysis, and density functional calculations data have been used to explain the possible reaction pathway of the ortho‐directed metathetical fluoride/amide exchange.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)