2026-05-05T20:49:00Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/497832025-02-21T12:04:35Zcom_10324_1186com_10324_931com_10324_894col_10324_1404

00925njm 22002777a 4500 dc Gioria, Estefania author Pozo, Juan del author Lledós, Agustí author Espinet Rubio, Pablo author 2021 The easily prepared hemilabile ligand 1-(PPh2),2-(trans-CH═CHCOPh)–C6F4 (PhPEWO-F) and other PEWO ligands are well-known promoters of C–C reductive eliminations and very effective in Negishi couplings. As an example, the efficient Negishi coupling of (C6F5)–I and Zn(C6F5)2 is reported. The thorough experimental study of the steps involved in the catalytic cycle uncovers the potential weakness of this ligand that could frustrate at some points the desired cycle and provide some simple precautions to keep the catalytic cycle working efficiently. Density functional theory (DFT) calculations complete the experimental study and provide insight into nonobservable transition states and intermediates, comparing the potential conflict between reductive elimination and olefin insertion. Our results showcase the importance the transmetalation step, facilitated by the strong trans effect of the electron-withdrawing ligand, and the choice of organozinc nucleophiles, critical to ensure fast group exchange and a positive outcome of the catalytic reactions. Organometallics, 2021, vol. 40, n. 14. p. 2272–2282 0276-7333 https://uvadoc.uva.es/handle/10324/49783 10.1021/acs.organomet.1c00001 Understanding the Use of Phosphine-(EWO) Ligands in Negishi Cross-Coupling: Experimental and Density Functional Theory Mechanistic Study