0000000000286063
AUTHOR
Sven-oliver Hauber
Aryldimethylsilyl Modified Hypersilanes
Aryldimethylsilyl-substituted hypersilanes ArSiMe2Hyp [Hyp =Si(SiMe3)3; Ar = Mes (3a), Bph (3b), Mph (3c), Pph (3d), Tph (3e); Dpp (3f); with Mes = 2,4,6-Me3C6H2, Bph = 2-PhC6H4, Mph = 2-MesC6H4, Pph = 2′,3′,4′,5′,6′-pentamethylbiphenyl2-yl, Tph = 2′,4′,6′-triisopropylbiphenyl-2-yl and Dpp = 2,6-Ph2C6H3] have been synthesized by a multi-step reaction starting from the readily available starting materials ArI and (thf)xKHyp. For this purpose the aryl iodides were first converted into the lithium aryls by lithium-halogen exchange with n-butyl lithium. A salt-metathesis reaction with SiMe2Cl2 gave the corresponding arylchlorodimethylsilanes (2a–e) in excellent yields. Finally, reaction of 2a–e…
Halogenomercury Salts of Sterically Crowded Triazenides - Convenient Starting Materials for Redox-Transmetallation Reactions
Diaryl-substituted triazenides Ar(Ar′)N3HgX [Ar/Ar′ = Dmp/Mph, X = Cl (2a), Br (3a), I (4a); Ar/Ar′ = Dmp/Tph, X = Cl (2b), I (4b) with Mph = 2-MesC6H4, Mes = 2,4,6-Me3C6H2, Tph = 2′,4′,6′-triisopropylbiphenyl-2-yl and Dmp = 2,6-Mes2C6H3] were synthesized by salt-metathesis reactions in ethyl ether from the readily available starting materials Ar(Ar′)N3Li and HgX2. 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)N3MX(thf) (5b: M = Mg, X = I; 6b: M = Yb, X = Cl) in good yield. All new compounds were characterized by melting poin…
Isostructural potassium and thallium salts of sterically crowded triazenes: a structural and computational study.
Because of their similar cationic radii, potassium and thallium(I) compounds are usually regarded as closely related. Homologous molecular species containing either K(+) or Tl(+) are very rare, however. We have synthesized potassium and thallium salts MN3RR' derived from the biphenyl- or terphenyl-substituted triazenes Tph2N3H (1a), Dmp(Mph)N3H (1b), Dmp(Tph)N3H (1c), and (Me4Ter)2N3H (1d) (Dmp=2,6-Mes 2C6H3 with Mes=2,4,6-Me3C6H2; Me4Ter=2,6-(3,5-Me2C6H3)2C6H3; Mph=2-MesC6H4; Tph=2-TripC6H4 with Trip=2,4,6-(i)Pr3C6H2). The potassium complexes 2a- d were obtained in almost quantitative yield from the reaction of 1a- d with potassium metal in n-heptane. Metalation of 1a- d with TlOEt afforde…