Alkinyloverbindungen von Übergangsmetallen, V. Mitteil.: Alkinylokomplexe von Kupfer

Abstract

Durch Umsetzung geeigneter Kupfer(I)‐Verbindungen mit den Alkalisalzen von Acetylen, Propin und Phenylacetylen in verflüssigtem Ammoniak unter Luft‐und Feuchtigkeitsausschluß werden Alkinylocuprate (I) vom Typ Me2[Cu(CC·R)3] und Me[Cu(CC·R)2] (MeK,Na; RH, CH3, C6H5) rein dargestellt. Die Eigenschaften und das reaktive Verhalten dieser hydrolysenempfindlichen Komplexe werden beschrieben. Durch Reaktion von [Cu(NH3)4] (NO3)2 in flüssigem Ammoniak mit KC⋮CH wird schwarzes, hochexplosives cuC2 erhalten. Bei den analogen Umsetzungen mit KCC·CH3 bzw. KCC·C6H5 erfolgt dagegen quantitative Reduktion des Cu(II) zu Cu(I), wobei als Oxydationsprodukte Hexadiin‐(2.4) bzw. Diphenylbutadiin gebildet werden.

“Click” Chemistry: Application of Copper Metal in Cu-Catalyzed Azomethine Imine–Alkyne Cycloadditions

“…On the other hand, Cu 2 O was a poor catalyst, whereas CuO was inactive in this respect (Table , entries 6 and 7). Somewhat expectedly, , replacement of the dipolarophile 2 { 1 } or Cu catalyst with the acetylide Cu– 2 { 1 } did not improve the conversion (Table , entries 8 and 9). To check the importance of a clean Cu surface devoid of patina, two experiments were carried out with Cu activated with 1 M H 2 SO 4 or 50% N 2 H 4 ·H 2 O .…”

“…In acetonitrile, 93% conversion was achieved. In the above solvents, formation of small amounts of bright yellow, insoluble CuCC–CO 2 Me (Cu– 2 { 1 }) , was observed. Complete conversion was obtained in EtOAc, toluene, CHCl 3 , and CH 2 Cl 2 .…”

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

“…(Arylethynyl)- and (alkylethynyl)copper(I) compounds usually form polymeric aggregates [(RC≡CCu) n ] of low solubility [200–201]. For example, X-ray powder diffraction studies have shown the insoluble yellow (phenylethynyl)copper(I) [(PhC≡CCu) n ] to consist of an infinite Cu–Cu ladder structure ( n = ∞) [184].…”

“…In 2010, the group of Heaney presented experimental evidence for the participation of dinuclear alkynylcopper(I) complexes in CuAAC reactions [ 87 ]. (Arylethynyl)- and (alkylethynyl)copper(I) compounds usually form polymeric aggregates [(RC≡CCu) n ] of low solubility [ 200 – 201 ]. For example, X-ray powder diffraction studies have shown the insoluble yellow (phenylethynyl)copper(I) [(PhC≡CCu) n ] to consist of an infinite Cu–Cu ladder structure ( n = ∞) [ 184 ].…”

Crystal Structures of Homoleptic Propynyloargentates AI[Ag(C3H3)2] with AI = Ag, Li, Na Solved and Refined from X‐ray Powder Diffraction Data

“…[5] About 50 years ago Nast and co-workers synthesized numerous metal alkynyl compounds. [6] Among them are homoleptic Cu I , [7] Ag I , [8] and Au I [9] alkynyls, which were mainly characterized by elemental analysis and IR spectroscopy: structural data were not reported. Based on this work, we reinvestigated homoleptic silver propynyls A I [Ag(C 3 H 3 ) 2 ] for A I = Ag, Li -Cs.…”