Synthesis and structural characterization of indium compounds with bidentate amide ligands

Indium trichloride reacts with 1 equivalent of MeN(SiMe2NMeLi)(2) to give t he dimer [ClIn(NMeSiMe2)(2)NMe](2) and with 4 equivalents of HNMeSiMe2NMeLi to give [Li{In(HNMeSiMe2NMe)(2)(MeNSiMe2NMe)}](2). In the structure of [Cl In(NMeSiMe2)(2)NMe](2) a chloride and one amide group of a [MeN(SiMe2NMe)(2 )](2-) ligand are bonded to each In atom in terminal positions and the othe r amide group of the chelating ligand is shared between two In atoms. The t erminal chlorides have an anti-ClIn ... InCl arrangement. The amine group o f the [MeN(SiMe2NMe)(2)](2-) ligand does not interact with In. Variable tem perature NMR spectra show [ClNn(NMeSiMe2)(2)NMe](2) undergoes a fluxional p rocess, and a mechanism involving bridge-terminal amide exchange is propose d to account for the data. The molecule [Li{In(HNMeSiMe2NMe)(2)(MeNSiMe2NM) }](2) has a Li2In2Si2N4 adamantane-like core and overall virtual D-2 symmet ry.