Journal
ACS CATALYSIS
Volume 12, Issue 7, Pages 4227-4241Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c05823
Keywords
gold catalysis; pi-complexes; ethylene functionalization; hydroamination; bulky phosphines
Categories
Funding
- European Research Council (ERC Starting Grant, CoopCat) [756575]
- Spanish Ministry of Science and Innovation [PID2019110856GA-I00]
- Spanish Ministry of Science and Innovation and Junta de Andalucia for postdoctora l programs [FJC2018-035514-I, DOC_00149]
- European Research Council (ERC) [756575] Funding Source: European Research Council (ERC)
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A series of gold(I)-ethylene pi-complexes containing bulky phosphine ligands have been synthesized, and the importance of these ligands in stabilizing the gold(I)-ethylene bond and preventing decomposition has been discovered. By improving the catalyst structure and reaction conditions, the catalytic performance in the hydroamination of ethylene can be enhanced.
A series of gold(I)-ethylene pi-complexes containing a family of bulky phosphine ligands has been prepared. The use of these sterically congested ligands is crucial to stabilize the gold(I)-ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. The precatalysts bearing the most sterically demanding phosphines showed the best results reaching full conversion to the hydroaminated products under notably mild conditions (1 bar of ethylene pressure at 60 degrees C). Kinetic analysis together with density functional theory calculations revealed that the assistance of a second molecule of the nucleophile as a proton shuttle is preferred even when using an extremely congested cavity-shaped Au(I) complex. In addition, we have measured a strong primary kinetic isotopic effect that is consistent with the involvement of X-H bond-breaking events in the protodeauration turnover-limiting step.
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