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revised on 06.05.2020 and posted on 08.05.2020by Nereida Hidalgo, Juan Jose Moreno, Marina Pérez-Jiménez, Celia Maya, Joaquin López-Serrano, Jesus Campos
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