PSb⁺P Ligand: Platform for a Stibenium to Transition-Metal Interaction

The coordination chemistry of cationic divalent pnictogen ligands, such as nitrenium and phosphenium, has been well-explored in recent years. However, corresponding studies of a heavier congener, stibenium ion, are rare. To better facilitate a Sb⁺-metal interaction, a tridentate P-Sb⁺-P ligand with two phosphine buttresses was designed and synthesized, and its coordination chemistry toward late transition metals was investigated. The stibenium ligand was delivered as an activated P(SbCl)P-AgOTf complex (2) that releases AgCl and the P-Sb⁺-P ligand upon the treatment with transition metals. Reacting 2 with Rh(I) and Ir(I) metals yielded the anticipated stibenium-transition-metal complexes [(Rh(COD)Cl)₂(μ-PSb⁺P)] OTf ([3][OTf]) and [(Ir(COD)Cl)₂(μ-PSb⁺P)] OTf ([4][OTf]). The M-Sb⁺-M bridging structure was confirmed by single-crystal X-ray crystallography, and the bonding situation was examined computationally. Theoretical studies revealed the presence of three-center delocalized M-Sb⁺-M bonding interactions in [3][OTf] and [4][OTf].