Recent efforts from our laboratory have shown that stibines behave as non-innocent ligands when bound to transition metals. For example, we have observed that triarylstibines bound to platinum react with incoming halide anions to generate stiboranyl ligands as shown in Figure 1. This event is accompanied by a formal reduction of the coordinated metal thus suggesting that chemistry at the antimony center could be used to electronically control the reactivity of the metal center. Taking this chemistry in reverse would suggest that decoordination of a halide from a halostiboranyl ligand could be used to make the coordinated metal center more oxidized and thus more electrophilic. In this presentation, we will present the results that we have obtained using a series of stiboranyl platinum complexes . In addition to investigating various strategies to abstract an anion from the antimony center, we have assessed the impact of these changes on the carbophilic reactivity of the platinum center. Our results show that halide abstraction from antimony affords cationic platinum complexes which catalyze enyne cycloisomerization reactions.

Lewis acidic antimony: Application as a non-innocent ligand for the activation of platinum catalyst

253rd National Meeting (2017)

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