Anion‐Controlled Switching of an X Ligand into a Z Ligand: Coordination Non‐innocence of a Stiboranyl Ligand

The tetravalent platinum stiboranyl complex [(o‐(Ph₂P)C₆H₄)₂(o‐C₆Cl₄O₂)Sb]PtCl₂Ph ( 2 ) has been synthesized by reaction of [(o‐(Ph₂P)C₆H₄)₂SbClPh]PtCl ( 1 ) with o‐chloranil. In the presence of fluoride anions, the stiboranyl moiety of 2 displays non‐innocent behavior and is readily converted into a fluorostiborane unit. This transformation, which is accompanied by elimination of a chloride ligand from the Pt center, results in the formation of [(o‐(Ph₂P)C₆H₄)₂(o‐C₆Cl₄O₂)SbF]PtClPh ( 3 ). Structural, spectroscopic, and computational studies show that the conversion of 2 into 3 is accompanied by a cleavage of the covalent Pt? Sb bond present in 2 and formation of a longer and weaker Pt→Sb interaction in 3 . These results show that this new Pt–Sb platform supports the fluoride‐induced metamorphosis of a stiboranyl X ligand into a stiborane Z ligand.