By performing combined XRD and theoretical studies, we established the modes of R^EWGI⋯I–Pt XBs with [Pt₂(μ-I)₂I₄]²⁻acting as an XB acceptor.

The observed and confirmed theoretically metal-involving halogen bond Ar–I⋯[d_z2Pt^II] provides experimental evidence favoring a XB formation step upon oxidative addition of ArI to Pt^II.

The complexes [RhX(COD)]₂ (X = Cl, Br; COD = 1,5-cyclooctadiene) form cocrystals with σ-hole iodine donors. X-ray diffraction studies and extensive theoretical considerations indicate that the d_z²-orbitals of two positively charged rhodium(I) centers provide sufficient nucleophilicity to form a three-center halogen bond (XB) with the σ-hole donors. The two metal centers function as an integrated XB acceptor, providing assembly via a metal-involving XB.