Article
Unveiling the Latent Reactivity of Cp* Ligands (C5Me5-) toward Carbon Nucleophiles on an Iridium Complex
Author/s | Pita Milleiro, Alejandra
Alférez, Macarena G. Moreno Díaz, Juan José Espada, María F. Maya Díaz, Celia María Campos, Jesús |
Department | Universidad de Sevilla. Departamento de Química Inorgánica |
Publication Date | 2023 |
Deposit Date | 2024-05-13 |
Published in |
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Abstract | The divergent reactivity of the cationic iridium complex [(η5-C5Me5)IrCl(PMe2ArDipp2)]+ (ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2) toward organolithium and Grignard reagents is described. The noninnocent behavior of the Cp* ... The divergent reactivity of the cationic iridium complex [(η5-C5Me5)IrCl(PMe2ArDipp2)]+ (ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2) toward organolithium and Grignard reagents is described. The noninnocent behavior of the Cp* ligand, a robust spectator in the majority of stoichiometric and catalytic reactions, was manifested by its unforeseen electrophilic character toward organolithium reagents LiMe, LiEt, and LinBu. In these unconventional transformations, the metal center is only indirectly involved by means of the Ir(III)/Ir(I) redox cycle. In the presence of less nucleophilic organolithium reagents, the Cp* ligand also exhibits noninnocent behavior undergoing facile deprotonation, which is also concomitant with the reduction of the metal center. In turn, the weaker alkylating agents EtMgBr and MeMgBr effectively achieve the alkylation of the metal center. These reactive iridium(III) alkyls partake in subsequent reactions: while the ethyl complex undergoes β-H elimination, the methyl derivative releases methane by a remote C-H bond activation. Computational studies, including the quantum theory of atoms in molecules (QTAIM), support that the preferential activation of the non-benzylic C-H bonds takes place via sigma-bond metathesis. |
Funding agencies | European Research Council (ERC) Ministerio de Ciencia e Innovación (MICIN). España Junta de Andalucía |
Project ID. | 756575
PID2019-110856GA-I00 P18-FR-4688 US-1380849 DOC_00153 |
Citation | Pita Milleiro, A., Alférez, M.G., Moreno Díaz, J.J., Espada, M.F., Maya Díaz, C.M. y Campos, J. (2023). Unveiling the Latent Reactivity of Cp* Ligands (C5Me5-) toward Carbon Nucleophiles on an Iridium Complex. Inorganic Chemistry, 62 (15), 5961-5961. https://doi.org/10.1021/acs.inorgchem.2c04381. |
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