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( t Bu Ar ≠ )(SiR 3 )] − ( t Bu Ar ≠ =2,6‐(CHPh 2 ) 2 ‐4‐ t BuC 6 H 2 , R=Me, Ph). The lithium and potassium amide salts showed different patterns of solvation and demonstrated that the Si Ph 3 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{ t Bu Ar ≠ }{SiPh 3 })Cl 2 using AlCl 3 afforded the 1:1 salt [Bi(N{ t Bu Ar ≠ }{SiPh 3 })Cl][AlCl 4 ]. 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{ t Bu Ar ≠ }{SiPh 3 })(Ph)Cl.