RT info:eu-repo/semantics/article
T1 Expanding the Concepts Trans Influence and Back-Donation: Hybrid and Side Donations in [Cp*MIII(L)XY] (M = Rh, Ir) Complexes with CO, CN–, and CNR Ligands. A Window to Cis Influence
A1 Fernández Moyano, Sara
A1 Peñas de Frutos, Marconi Nicolás
A1 Bartolomé Albistegui, María del Camino
A1 Espinet Rubio, Pablo
K1 X-rays
K1 Rayos X
K1 Metals
K1 Metales
K1 Ligands
K1 Ligandos
K1 Molecules
K1 Moléculas
AB Analysis of the bonding contributions in molecules [MIIICp*(L)XY] (M = Rh, Ir; Cp* = C5Me5; L = CO, CN–, CNR) has uncovered a rich variety of types of interaction that seem to have escaped detection so far, in spite of the continuous popularity of cyclopentadienyl transition-metal complexes since the 1970s. At variance with the M—C≡O bond in square-planar systems, which shows typical metal-to-CO π-back-donation, the nonorthogonal arrangement of the Cp* plane and Rh—C≡O fragment and the pseudooctahedral geometry lead to the observation of many direct lateral donations from other ligands that do not involve the metal orbitals, and we name side donations, for instance, Cp* → π*(CO), Cl → π*(CO), and F → π*(CO). Hybrid donations partially involving the metal, M–Caryl → π*(CO), are also observed. The summation of multiple contributions other than back-donation can easily account for about 20% of the electron donation to the π*(C≡O) orbitals.
PB ACS Publications
SN 0020-1669
YR 2021
FD 2021
LK https://uvadoc.uva.es/handle/10324/49775
UL https://uvadoc.uva.es/handle/10324/49775
LA eng
NO Inorganic Chemistry, 2021, vol. 60, n. 18. p. 14410-14417
NO Producción Científica
DS UVaDOC
RD 22-dic-2024