Dicoordinate Au(I)–ethylene complexes as hydroamination catalysts Miquel Navarro, Macarena G. Alférez, Juan Miranda-Pizarro, Juan J. Moreno, Jesús Campos Universidad de Sevilla, Spain p-Complexes of gold are generally proposed as key intermediates in the functionalization of alkenes, alkynes, dienes or allenes in a wide range of catalytic processes. [1] Thus, the isolation of gold p-complexes holds an intrinsic interest associated with their catalytic relevance and has provided valuable insights during the last years. Cationic gold(I) p-complexes of substituted alkenes have been stabilized by monodentate and bidentate ligands. However, despite significant synthetic efforts, dicoordinate ethylene complexes remain unknown and only by using N- and P-based bidentate ligands the related tricoordinate gold(I) p-ethylene adducts. [2] The use of bulky phosphine ligands has allowed the stabilization, isolation and complete characterization of the first dicoordinate gold(I)–ethylene adducts. [3] The bonding situation of these species has been investigated by means of state-of-the-art Density Functional Theory (DFT) calculations. In addition, the lability of the gold- ethylene bond has also been interrogated. For instance, the use of these sterically congested ligands have proved crucial to stabilize the gold(I)–ethylene bond and prevent decomposition, boosting up their catalytic performance in the highly underexplored hydroamination of ethylene. [4] As a result, the precatalysts bearing the most sterically demanding phosphines showed excellent results reaching full conversion to the hydroaminated products under notably mild conditions, highlighting the high catalytic potential of very sterically crowded catalysts. References 1. G. Dyker. Angew. Chem. Int. Ed. 2000 , 39 , 4237; b) A. S. K. Hashmi, Gold Bull. 2004 , 37 , 51. 2. M. Navarro, D. Bourissou. Adv. Organomet. Chem. 2021 , 76 , 101. 3. J. Keller, C. Schlierf, C. Nolte, P. Mayer, B. F. Straub. Synthesis 2006 , 2 , 354; b) M. Navarro, J. Miranda-Pizarro, J. J. Moreno, C. Navarro-Gilabert, I. Fernández, J. Campos. Chem. Commun. 2021 , 57 , 9280. 4. Z. Zhang, S. D. Lee, R. A. Widenhoefer. J. Am. Chem. Soc. 2009 , 131 , 5372; b) M. Navarro, M. G. Alférez, M. de Sousa, J. Miranda-Pizarro, J. Campos. ACS Catal. 2022 , 12 , 4227.
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