Intramolecular Metal-Arene Interactions in Neutral and Cationic Main Group Compounds

The role of intramolecular metal-arene interactions has been investigated in the solid-state structures of a series of main group compounds supported by the bulky amide ligands, [N(Ar-tBu)(SiR3)](-) (Ar-tBu=2,6-(CHPh2)(2)-4-tBuC(6)H(2), R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the SiPh3 substituent is able to be involved in stabilizing the electrophilic metal. These group 1 metal compounds served as ligand transfer reagents to access a series of bismuth(III) halides. Chloride extraction from Bi(N{Ar-tBu}{SiPh3})Cl-2 using AlCl3 afforded the 1:1 salt [Bi(N{Ar-tBu}{SiPh3})Cl][AlCl4]. This was accompanied by a significant rearrangement of the stabilizing -arene contacts in the solid-state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl-transfer and generation of the neutral Bi(N{Ar-tBu}{SiPh3})(Ph)Cl.