2024-03-29T14:53:52Zhttps://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/497752021-11-08T21:46:40Zcom_10324_1186com_10324_931com_10324_894col_10324_1404
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
Fernández Moyano, Sara
Peñas de Frutos, Marconi Nicolás
Bartolomé Albistegui, María del Camino
Espinet Rubio, Pablo
X-rays
Rayos X
Metals
Metales
Ligands
Ligandos
Molecules
Moléculas
Producción Científica
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.
Junta de Castilla y León (project VA224P20)
Ministerio de Economía, Industria y Competitividad (project CTQ2017-89217- P)
Ministerio de Ciencia, Innovación y Universidades (project PID2020-118547GB-I00)
Irish Research Council (postdoctoral fellowship GOIPD/2020/701)
2021-11-08T10:52:40Z
2021-11-08T10:52:40Z
2021
info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Inorganic Chemistry, 2021, vol. 60, n. 18. p. 14410-14417
0020-1669
https://uvadoc.uva.es/handle/10324/49775
10.1021/acs.inorgchem.1c02189
eng
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c02189
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-nd/4.0/
© 2021 American Chemical Society
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ACS Publications
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http://creativecommons.org/licenses/by-nc-nd/4.0/
UVaDOC. Repositorio Documental de la Universidad de Valladolid
https://uvadoc.uva.es/handle/10324/49775