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(tBuAr≠)(SiR3)]− (tBuAr≠=2,6‐(CHPh2)2‐4‐tBuC6H2, 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{tBuAr≠}{SiPh3})Cl2 using AlCl3 afforded the 1:1 salt [Bi(N{tBuAr≠}{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{tBuAr≠}{SiPh3})(Ph)Cl.