Reactivity of the tetraphenyldithioimidodiphosphine-diiodine (HL•I2) adduct towards indium powder

The reaction of indium powder with the mixture (SPPh2)(2)NH and I-2 (HL.I-2) in Et2O at room temperature gave the indium(III) complex InLI2 (1). The reaction occurs in two steps, the first of which leads to the formation of InI3 and free HL, then the subsequent reaction between these species yields compound 1, H+, and the anion InI4-. The crystal lattice of I is made up of neutral acentric molecules where the metal ion is bonded through two sulfur atoms to one anionic (SPPh2)(2)N- (L) ligand and two iodide ions. The central In-III ion shows a slightly distorted tetrahedral coordination geometry. Density functional theory (DFT) calculations, carried out at the B3LYP level, have been used to interpret the electrochemical behaviour of 1.