Abstract
The capacity of the imido‐nitrido organometallic ligand [{Ti(η^5^‐C~5~Me~5~)(μ‐NH)}~3~(μ~3~‐N)] (1) to entrap main group metal halides MX~n~ has been investigated. Treatment of 1 with metal halides in toluene or dichloromethane afforded several soluble adducts [MX~n~(L)] (L=1) in good yields. The reaction of 1 with one equivalent of Group 1 and 13 monohalides MX afforded single cube‐type complexes [XM{(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] (M=Li, X=Br (2), I (3); M=Na, X=I (4); M=In, X=I (5); M=Tl, X=I (6)). Analogous treatment of 1 with Group 2 and 14 dihalides MX~2~ gave the corresponding adducts [I~2~M{(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] (M=Mg (7), Ca (8), Sr (9)) and [Cl~2~M{(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}] (M=Sn (10), Pb (11)). The treatment of 1 with SnI~2~ or the reaction of 10 with MeI at 60 °C afforded two azametallocubane units linked by two bridging iodine atoms [{ISn(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)}~2~(μ‐I)~2~] (12). Indium triiodide reacted with 1 in toluene to form the adduct [I~3~In(μ~3~‐NH)~3~Ti~3~(η^5^‐C~5~Me~5~)~3~(μ~3~‐N)] (13). Density functional theory calculations have been carried out to study these processes and evaluate the influence of the solvent. X‐ray crystal structure determinations have been performed for complexes 10, 12, and 13.