Reactivity of the tetraphenyldithioimidodiphosphine–diiodine (HL·I2) adduct towards indium powder

Abstract

The reaction of indium powder with the mixture (SPPh₂)₂NH and I₂ (HL·I₂) 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 1 is made up of neutral acentric molecules where the metal ion is bonded through two sulfur atoms to one anionic (SPPh₂)₂N⁻ (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.