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

The indium tris(amide)s [(Et 2 N) 3– n In{N(C 6 F 5 )(2‐C 5 H 4 N)} n ] [ n = 1 ( 15 ), 2 ( 16 ) or 3 ( 9 )] have been prepared by treatment of [In(NEt 2 ) 3 ] 2 ( 3 ) with a stoichiometric amount of (2‐C 5 H 4 N)(C 6 F 5 )NH ( 1 ). The analogous reaction of Bi(NMe 2 ) 3 ( 2 ) with 3 equiv. of amine 1 and the treatment of BiCl 3 ( 5 ) with a stoichiometric amount of (2‐C 5 H 4 N)(C 6 F 5 )NLi ( 4 ) both lead to [Bi{N(C 6 F 5 )(2‐C 5 H 4 N)} 3 ] ( 10 ). In contrast, only the difluoride 11 or the monofluoride 12 , which are the products of intramolecular ortho ‐directed exchange of NMe 2 and F substituents, are obtained from the reaction of 2 with 1 or 2 equiv. of 1 , respectively. The reaction between Me 3 Sb(Hal) 2 [Hal = Br ( 7 ) Cl, ( 8 )] and 1 or 2 equiv. of lithium salt 4 gives the corresponding stable monoamides [Me 3 (Hal)Sb{N(C 6 F 5 )(2‐C 5 H 4 N)}] [Hal = Br ( 17 ), Cl ( 18 )] or bis(amide) [Me 3 Sb{N(C 6 F 5 )(2‐C 5 H 4 N)} 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)