Diaryliodonium Tetrachloroplatinates(II): Recognition of a Trifurcated Metal-Involving μ₃-I···(Cl,Cl,Pt) Halogen Bond

Synthesis and X-ray characterization of the four diaryliodonium tetrachloroplatinates(II) [Ar1Ar2I]2[PtCl4] (Ar1/Ar2 = Ph/Ph (1), 4-Cl-C6H4/2,4,6-(MeO)3C6H2 (2), 4-Me-C6H4/2,4,6-(MeO)3C6H2 (3), Ph/2,4,6-(MeO)3C6H2 (4)) allowed deterimination several types unconventional halogen-bond (HaB) patterns. The first example a metal-involved trifurcated four-center μ3-X···(X′,X′,M) HaB is represented by metal-involving I···Pt (the structure 4) with iodonium cations acting as donors, which supported two weak I···Cl contacts. structures 1–3 display bifurcated three-center μ2-I···(Cl,Cl) HaBs cations. DFT calculations were used to estimate energetic features Molecular electrostatic potential (MEP) surfaces noncovalent interaction plot index (NCIPlot) computational tools evaluate σ-holes characterize HaBs, respectively, in all structures.