Halogenomercury Salts of Sterically Crowded Triazenides – Convenient Starting Materials for Redox‐Transmetallation Reactions

Diaryl‐substituted triazenides Ar(Ar′)N 3 Hg X [Ar/Ar′ = Dmp/Mph, X = Cl ( 2a ), Br ( 3a ), I ( 4a ); Ar/Ar′ = Dmp/Tph, X = Cl ( 2b ), I ( 4b ) with Mph = 2‐MesC 6 H 4 , Mes = 2,4,6‐Me 3 C 6 H 2 , Tph = 2′,4′,6′‐triisopropylbiphenyl‐2‐yl and Dmp = 2,6‐Mes 2 C 6 H 3 ] were synthesized by salt‐metathesis reactions in ethyl ether from the readily available starting materials Ar(Ar′)N 3 Li and Hg X 2 . These compounds may be used for redox‐transmetallation reactions with rare‐earth or alkaline earth metals. Thus, reaction of 4b or 2b with magnesium or ytterbium in tetrahydrofuran afforded the triazenides Dmp(Tph)N 3 MX (thf) ( 5b : M = Mg, X = I; 6b : M = Yb, X = Cl) in good yield. All new compounds were characterized by melting point, 1 H and 13 C NMR spectroscopy and for selected species by IR spectroscopy or mass spectrometry. In addition, the solid‐state structures of triazenides 2a , 2b , 3a , 4b , 5b and 6b were investigated by single‐crystal X‐ray diffraction.