RT info:eu-repo/semantics/article
T1 A copper-masked monosubstituted carbene as a general transmetalating agent toward stable carbene complexes
A1 Álvarez, María
A1 Villalba de Pando, Francisco
A1 Casciotti, Martina
A1 Molina, Francisco
A1 Sciortino, Giuseppe
A1 Lledós, Agustí
A1 Albéniz Jiménez, Ana Carmen
A1 Belderrain, Tomás R.
A1 Pérez, Pedro J.
K1 Química
K1 carbene
K1 transition metal
K1 2303 Química Inorgánica
AB 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.
PB Cell Press
SN 2451-9294
YR 2024
FD 2024
LK https://uvadoc.uva.es/handle/10324/75094
UL https://uvadoc.uva.es/handle/10324/75094
LA eng
NO Chem, 2024, 10, 1576-1592
NO Producción Científica
DS UVaDOC
RD 23-feb-2025