Kupfer‐ und Silber‐Carbenkomplexe ohne Heteroatom‐Stabilisierung: Struktur, Spektroskopie und relativistische Effekte

Abstract

À liegen zwischen denen des isostrukturellen Silberkomplexes und denen des schon beschriebenen smaragdgrünen Goldcarben-Komplexes.E in Vergleichd er Elemente der Kupfertriade weist darauf hin, dass relativistische Effekte für die starke s-Bindung und die signifikante pRückbindung in der Goldcarben-Einheit verantwortlichs ind.

Silver(I)‐Catalyzed N‐Trifluoroethylation of Anilines and O‐Trifluoroethylation of Amides with 2,2,2‐Trifluorodiazoethane

“…classic metal carbene N À Hi nsertions. [17,20,22] However,s uch mechanism seems less likely in view of the control experiment results as well as the O-trifluoroethylation in the case of amide under the similar reaction conditions.…”

ChemInform Abstract: Silver(I)‐Catalyzed N‐Trifluoroethylation of Anilines and O‐Trifluoroethylation of Amides with 2,2,2‐Trifluorodiazoethane.

“…Chemie classic metal carbene N À Hi nsertions. [17,20,22] However,s uch mechanism seems less likely in view of the control experiment results as well as the O-trifluoroethylation in the case of amide under the similar reaction conditions.…”

“…[21,22] Migratory insertion of the amine ligand to the carbenic carbon atom gives the intermediate C,f rom which protonation affords the Ntrifluoroethylated product 2.F or O-trifluoroethylation of amides,asimilar mechanism is proposed. Thea niline derivatives 1 firstly react with Ag + to form the Ag I /aniline complex A.T hen, the reaction of CF 3 CHN 2 with A produces the Ag I /carbene intermediate B.…”

“…[17,20,22] However,s uch mechanism seems less likely in view of the control experiment results as well as the O-trifluoroethylation in the case of amide under the similar reaction conditions. [17,20,22] However,s uch mechanism seems less likely in view of the control experiment results as well as the O-trifluoroethylation in the case of amide under the similar reaction conditions.…”

“…Thea niline derivatives 1 firstly react with Ag + to form the Ag I /aniline complex A.T hen, the reaction of CF 3 CHN 2 with A produces the Ag I /carbene intermediate B. [21,22] Migratory insertion of the amine ligand to the carbenic carbon atom gives the intermediate C,f rom which protonation affords the Ntrifluoroethylated product 2.F or O-trifluoroethylation of amides,asimilar mechanism is proposed. In this case,the Ag I / imidate complex A' is favored because of the relatively hard basicity of the oxygen atom relative to the nitrogen atom.…”