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

preprint
revised on 06.05.2020 and posted on 08.05.2020 by 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 characterized.

Funding

European Research Council (ERC Starting Grant, CoopCat, Project 756575)

Spanish Ministry of Economy and Competitiveness (Project CTQ2016-75193-P [AEI/ FEDER, UE])

History

Email Address of Submitting Author

jesus.campos@iiq.csic.es

Institution

Spanish National Research Council (CSIC)-University of Sevilla

Country

Spain

ORCID For Submitting Author

0000-0002-5155-1262

Declaration of Conflict of Interest

There are no conflicts of interest to declare for any of the authors.

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