Stepwise Introduction of Thiolates in Copper−Indium Binuclear Complexes

We report the synthesis and characterization of copper−indium binuclear I−III complexes composing the series (Ph3P)2CuIn(SEt)xCl4−x (1−5; 0 ≤ x ≤ 4). Members of the series, which are prepared by variations in the stoichiometry, are compared in terms of their solid-state structures, spectroscopic features, and suitability as precursors for CuInS2 materials. The regiochemistry of thiolate substitution, the preference for monomeric versus dimeric (eight-membered ring) structures, and new synthetic strategies informed by this series are all discussed.