Modulating the σ-Accepting Properties of an Antimony Z-type Ligand via Anion Abstraction: Remote-Controlled Reactivity of the Coordinated Platinum Atom.

In search of ligand platforms, which can be used to remotely control the catalytic activity of a transition metal, we have investigated the coordination noninnocence of ambiphilic L/Z-type ligands containing a trifluorostiborane unit as a Lewis acid. The known dichlorostiboranyl platinum complex (( o-(PhP)CH)SbCl)PtCl (1) reacts with TlF in the presence of acetonitrile (MeCN) and cyclohexyl isocyanide (CyNC) to afford the trifluorostiborane platinum complexes 2 ((( o-(PhP)CH)SbF)Pt-NCMe) and 3 ((( o-(PhP)CH)SbF)Pt-CNCy), respectively. Formation of these complexes, which results from a redistribution of the halide ligands about the dinuclear core, affects the nature of the Pt-Sb bond. The latter switches from covalent in 1 to polar covalent (or dative) in 2 and 3 where the trifluorostiborane moiety engages the platinum center in a Pt → Sb interaction. The polarity of the Pt-Sb bond can be modulated further by abstraction of an antimony-bound fluoride ligand using B(CF). These reactions afford the cationic complexes [(( o-(PhP)CH)SbF)Pt-NCMe] ([5]) and [(( o-(PhP)CH)SbF)Pt-CNCy] ([6]) which have been isolated as [BF(CF)] salts. These complexes possess a highly Lewis acidic difluorostibonium moiety, which exerts an intense draw on the electron density of the platinum center. As a result, the latter becomes significantly more electrophilic. In the case of [5], which contains a labile acetonitrile ligand, this increased electrophilicity translates into increased carbophilicity as reflected by the ability of this complex to promote enyne cyclization reactions. These results demonstrate that the coordination noninnocence of antimony Z-ligands can be used to adjust the catalytic activity of an adjoining metal center.