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.