2026-05-12T18:51:06Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/750942025-02-21T07:22:59Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

A copper-masked monosubstituted carbene as a general transmetalating agent toward stable carbene complexes Álvarez, María Villalba de Pando, Francisco Casciotti, Martina Molina, Francisco Sciortino, Giuseppe Lledós, Agustí Albéniz Jiménez, Ana Carmen Belderrain, Tomás R. Pérez, Pedro J. Química Producción Científica Metal complexes bearing carbene ligands LnM=CR1R2 are relevant in- termediates in catalytic transformations. The stability of isolated car- bene complexes decreases for the case of monosubstituted carbenes (R1 = H). We have discovered that the copper complex [TpMsCu(C(H) NEt2)] (1) readily transfers the aminocarbene :C(H)NEt2 to other com- plexes of metals, such as rhodium, iridium, palladium, platinum, copper, or gold, leading to complexes bearing the M–C(H)NEt2 moiety. Exper- imental data allow us to propose that this monosubstituted aminocar- bene (MAC) ligand displays a nucleophilicity similar to that of NHC (N-Heterocyclic Carbene) ligands bearing bulky substituents but it has a considerably lower volume. These features allow unprecedented reac- tivity patterns, such as the generation of the first stable monosubsti- tuted carbene adduct of Rh2(OAc)4, a well-known catalyst for carbene transfer reactions. Density functional theory (DFT) studies carried out on the transfer of the MAC ligand from [TpMsCu(C(H)NEt2)] to trans- [PdCl2(NCMe)(PPh3)] led us to ascertain that the transmetalation pro- cess involves several intermediates in which the TpMs ligand shifts be- tween the k2 and k3 coordination modes. 2025-02-20T19:44:26Z 2025-02-20T19:44:26Z 2024 info:eu-repo/semantics/article Chem, 2024, 10, 1576-1592 2451-9294 https://uvadoc.uva.es/handle/10324/75094 10.1016/j.chempr.2024.03.009 1576 5 1592 Chem 10 eng https://www.sciencedirect.com/science/article/abs/pii/S2451929424001189 info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 Internacional Cell Press SI