Bis(amidodimethyl)disiloxane ligands derived from O{SiMe2N(H)R}2 (abbreviated as (NONR)H2) are a stable support for neutral and cationic bismuth compounds. Attempts to extend the series Bi(NONR)Cl (R = Ar = 2,6-iPr2C6H3; R = tBu) to include compounds where R = Ar' = 2,6-Me2C6H3 were complicated by concomitant formation of the bimetallic compound {Bi(NONAr')}2(μ-NONAr'). Compounds containing [Bi(NONR)]+ cations were obtained from reactions with group 13 chlorides MCl3 (M = Al, Ga). X-ray crystallographic analysis showed intermolecular interactions with the [MnCl(3n+1)] anion.