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

The role of intramolecular metal⋅⋅⋅π-arene interactions has been investigated in the solid-state structures of a series of main group compounds supported by the bulky amide ligands, [N(^tBu Ar^≠ )(SiR₃ )]^- (^tBu Ar^≠ =2,6-(CHPh₂ )₂ -4-tBuC₆ H₂ , 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{^tBu Ar^≠ }{SiPh₃ })Cl₂ using AlCl₃ afforded the 1:1 salt [Bi(N{^tBu Ar^≠ }{SiPh₃ })Cl][AlCl₄ ]. This was accompanied by a significant rearrangement of the stabilizing π-arene contacts in the solid-state. Attempted preparation of the corresponding tetraphenylborate salt resulted in phenyl-transfer and generation of the neutral Bi(N{^tBu Ar^≠ }{SiPh₃ })(Ph)Cl.