Heterometallic complexes of trivalent copper dithiocarbamate with indium and gallium chloride

Heterometallic Cu−In and Cu−Ga complex salts, [Cu(III)(dedtc)₂][In(III)Cl₄] (1) and [Cu(III)(dedtc)₂][Ga(III)Cl₄] (2) (dedtc = ⁻S₂CNEt₂, diethyldithiocarbamate), were synthesized from Cu(II)(dedtc)₂, In(III)Cl₃, and Ga(III)I₃ in dichloromethane and acetone solvents. The trivalent copper complex [Cu(III)(dedtc)₂]⁺ was produced by an oxidation reaction of Cu(II)(dedtc)₂ and [M(III)Cl₄]^– (M = In, Ga) which exhibit a blue-shift of the C–N vibrational mode resulting from the high oxidation state of copper(III) cations. In the Cu−Ga complex salt (2), [Ga(III)Cl₄]^– was obtained by a halogen exchange reaction between Ga(III)I₃ and CH₂Cl₂. Cu−In and Cu−Ga complex single crystals were grown in benzene and dichloromethane media. Their crystal structures were confirmed that [Cu(III)(dedtc)₂]⁺ units formed distorted octahedral structures with infinite polymeric Cu–S chains surrounded by dimeric [M(III)Cl₄]^– and benzene. The crystal structures of 1 and 2 included benzene as a guest molecule due to strong noncovalent interactions of metal chloride anions.