Effect of Ligands on the Lewis Acidity of the Metal and the Binding of N-Bases to Iridium Pincer Complexes

Osipova, E.S.; Gulyaeva, E.S.; Filippov, O.A.; Safronov, S.V.; Pavlov, A.A.; Polukeev, A.V.; Kirkina, V.A.; Titova, E.M.; Shubina, E.S.; Belkova, N.V.

Авторы: Osipova Elena S., Gulyaeva Ekaterina S., Filippov Oleg A., Safronov Sergey V., Pavlov Alexander A., Polukeev Alexey V., Kirkina Vladislava A., Titova Ekaterina M., Shubina Elena S., Belkova Natalia V.
Журнал: European Journal of Inorganic Chemistry
Том: 2019
Номер: 10
Год издания: 2019
Издательство: John Wiley & Sons Ltd.
Местоположение издательства: United Kingdom
Первая страница: 1389
Последняя страница: 1397
DOI: 10.1002/ejic.201801341
Аннотация: The coordination of pyridine (Py) and benzonitrile (PhCN) to benzene based pincer hydridochlorides [(PCP)IrH(Cl)] (1), [(POCOP)IrH(Cl)] (2), [{EtO(O)C‐POCOP}IrH(Cl)] (3), and [(PCN)IrH(Cl)] (4) was studied spectroscopically and computationally to deduce the ligand influence. The variable temperature NMR (1H, 31P, 15N) and UV/Visible spectroscopic measurements revealed preferential coordination of these N‐donor ligands in the apical position of 1–4 and gave the formation enthalpies for the hexacoordinate complexes, which follow the order: 1 ≈ 4 > 3 > 2. This order nicely agrees with the order of Lewis acidity obtained for these complexes in DFT calculations. The orbital and electron density distribution analysis were performed at the DFT/M06 theory level for 1–4 and a series of p‐substituted PCP‐based hydridochlorides. The increasing Lewis acidity of iridium [as a maximum energy, VS,max, of molecular electrostatic potential (MEP)] correlates with decreasing basicity of Cl‐ligand (as MEP minimum, VS,min) as well as with Hammett σp parameters of p‐substituents. Importantly, these properties are conserved upon conversion into the corresponding dihydrides, as shown on the example of 1 and 4.
Добавил в систему: Осипова Елена Сергеевна

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Effect of Ligands on the Lewis Acidity of the Metal and the Binding of N-Bases to Iridium Pincer Complexesстатья

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