Heteroleptic Iminophosphonamide In(III) Complexes: Source of Mild Lewis Acid Indium Centers

New In(III) complexes with iminophosphonamide ligand are reported for the first time. Reaction of the lithium iminophosphonamide, LLi⋅2OEt 2 with InCl 3 afforded the heterobimetallic compound, LInCl(μ‐Cl) 2 Li⋅2OEt 2 ( 1 ) (L=(2,6‐iPr 2 C 6 H 3 N)P(Ph 2 )(NtBu)). To prevent the formation of LiCl adduct in 1 , and to obtain the targeted LInCl 2 molecule, potassium salt of the ligand LK was reacted with InCl 3 that gave the adduct LInCl 2 (THF) ( 2 ). Formation of compounds 1 and 2 can be considered an outcome of the In(III) centers to exhibit Lewis acidity. Reaction of LK with InCl 3 in non coordinating solvent toluene gave the dimer [LInCl(μ‐Cl)] 2 ( 3 ) and its further treatment with Ph 2 P(=O)NHtBu afforded the adduct, LInCl 2 ⋅(O=P(Ph 2 )NHtBu) ( 4 ). Formation of the dimer 3 or the adduct 4 are again the reminiscent of the Lewis acid tendency of In(III) centers. Complexes 1–4 have been characterized using multinuclear NMR and HRMS. The single crystal X‐ray structures of 1 , 3 and 4 have also been elucidated.