Tuning Activity and Selectivity During Alkyne Activation by Gold(I)/Platinum(0) Frustrated Lewis Pairs

Abstract

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only frustrated systems based on Au(I)/Pt(0) combinations and their reactivity towards alkynes. We have inspected the activation of the simplest alkyne, namely acetylene, as well as of other internal and terminal triply bonded hydrocarbons. The gold(I) fragments are stabilized by three bulky phosphines bearing terphenyl groups. We have observed that subtle modifications on the substituents of these ligands proved critical to control the regioselectivity of acetylene activation and the product distribution resulting from C(sp)—H cleavage of phenylacetylene. A mechanistic picture based on experimental observations and computational analysis is provided. As a result of the cooperative action of the two metals of the frustrated pairs, several uncommon heterobimetallic structures have been fully characterized.