1,3-Bis(thiophosphinoyl)indene: A Unique and Versatile Scaffold for Original Polymetallic Complexes

The coordination of tridentate ligands featuring lateral coordination sites prone to acting as bridging ligands was explored with the aim of obtaining original polymetallic species in a straightforward and controlled manner. Accordingly, the 2-indenylidene chloropalladate [{Ind(Ph₂PS)₂}PdCl]⁻ was found to behave as a κ²-C,S bidentate ligand toward metal fragments, giving access to homo- and heteropolymetallic complexes. X-ray diffraction analyses reveal the presence of short metal–metal contacts in all of these complexes. Density functional theory calculations unambiguously substantiate that the metals engage in unusual d⁸···d⁸ interactions with a quasi-perpendicular arrangement of their coordination planes.