The Role of Non-Covalent Interactions in the Reactions between Palladium Hydrido Complex with Amidoarylphosphine Pincer Ligand and Brønsted Acids

Kirkina, V.A.; Kulikova, V.A.; Gutsul, E.I.; Gafurov, Z.N.; Sakhapov, I.F.; Yakhvarov, D.G.; Nelyubina, Y.V.; Filippov, O.A.; Shubina, E.S.; Belkova, N.V.

Авторы: Kirkina Vladislava A., Kulikova Vasilisa A., Gutsul Evgenii I., Gafurov Zufar N., Sakhapov Ilias F., Yakhvarov Dmitry G., Nelyubina Yulia V., Filippov Oleg A., Shubina Elena S., Belkova Natalia V.
Журнал: INORGANICS
Том: 11
Номер: 5
Год издания: 2023
Издательство: Molecular Diversity Preservation International (MDPI)
Местоположение издательства: Basel, Switzerland
Номер статьи: 212
DOI: 10.3390/inorganics11050212
Аннотация: The interaction between (PNP)PdH (1); PNP = bis(2-diisopropylphosphino-4-methylphenyl)amide and different acids (CF3SO3H, HBF4∙Et2O, fluorinated alcohols and formic acid) was studied in benzene or toluene as well as in neat alcohols by IR and NMR spectroscopies. The structures of hydrogen-bonded complexes were also optimized at the DFT/ωB97-XD/def2-TZVP level. The nitrogen atom of the amidophosphine pincer ligand readily accepts proton not only from strong Brønsted acids but from relatively weak fluorinated alcohols. That suggests that binding to palladium(II) increases the diarylamine basicity, making it a strong base. Nevertheless, H+ can be taken from [(PN(H)P)PdH]+ (2) by pyridine or hexamethylphosphoramide (HMPA). These observations confirm the need for a shuttle base to form [(PN(H)P)PdH]+ (2) as the result of the heterolytic splitting of H2 by [(PNP)Pd]+. At that, a stoichiometric amount of formic acid protonates a hydride ligand yielding an unstable η2-H2 complex that rapidly converts into formate (PNP)Pd(OCHO), which loses CO2 to restore (PNP)PdH, whereas the relatively high acid excess hampers this reaction through competitive protonation at nitrogen atom.
Добавил в систему: Астахов Григорий Сергеевич

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The Role of Non-Covalent Interactions in the Reactions between Palladium Hydrido Complex with Amidoarylphosphine Pincer Ligand and Brønsted Acidsстатья

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