Group 1 Complexes of an (Amido-amino)silane and Their Use in the Synthesis of the Bi(III) Amide, Bi(Me2Si{NAr}{N(H)Ar})Cl2 (Ar = 2,6‑i‑Pr2C6H3)

The synthesis of sodium and potassium salts of the monoanionic, (amido-amino)­silane, [Me2Si­{NAr}­{N­(H)­Ar}]− (Ar = 2,6-i-Pr2C6H3), and their use as ligand transfer reagents to bismuth are presented. Initial attempts to form Li­(Me2Si­{NAr}­{N­(H)­Ar) (2) using equimolar amounts of n-BuLi and the neutral compound Me2Si­{N­(H)­Ar}2 (1) gave mixtures of the unreacted di­(amino)­silane and the known dianion, Li2(Me2Si­{NAr}2), on workup. Reaction of 1 with NaH and KH, however, afforded the desired anion in the soluble, crystalline compounds Na­(Me2Si­{NAr}­{N­(H)­Ar})­(THF)3 (3(THF)3) and K­(Me2Si­{NAr}­{N­(H)­Ar}) (4). The crystal structure of 4 shows a cyclic hexamer [4]6, containing intra- and intermolecular K···π-aryl interactions. Reaction of 3 or 4 with BiCl3 demonstrated that both compounds are effective ligand transfer reagents, affording the bismuth compound Bi­(Me2Si­{NAr}­{N­(H)­Ar})­Cl2 (5). The crystal structure of 5 showed a primary monodentate κ1-N-bonding mode for the ligand with a close Bi···N contact to the neutral amino nitrogen atom. Long range Bi···Cl interactions associate these molecules into dimers, [5]2.