Coordination of SnCl3− ligands to {Cp*M}2+ (M = Rh, Ir)

•Reactions of [Cp*MCl2]2 (M = Rh, Ir) with SnCl2 give [Cp*M(SnCl3)3]− anions.•Characterized with X-ray, 119Sn, 13C, 1H NMR and DFT calculations.•Quantum-chemical calculations reveal covalent M-SnCl3 bonding.

Complexes [Cp*MCl2]2 (M = Rh, Ir) react with SnCl2·2H2O in CH2Cl2/MeOH with the formation of [Cp*MCl3-n(SnCl3)n]2− species (n = 1, 2, 3). The reactions were studied with 1H, 13C, 119Sn NMR techniques. Despite the presence of several species in the solution only a 1:3 complex [Cp*2Rh2(μ-Cl)3][Cp*Rh(SnCl3)3] ([1]) was crystallized and characterized by x-ray diffraction. Analogous iridium complex was crystallized with iridicinium cation as [Cp*2Ir][Cp*Ir(SnCl3)3] [2]. Electronic structure of new organometallic complexes was studied with DFT calculations. M-Sn bonding was shown to be essentially covalent by ELF method.

Graphical abstractStructure of [Cp*Rh(SnCl3)3]− anion.Figure optionsDownload full-size imageDownload as PowerPoint slide