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The interaction between (PNP)PdH (<b>1</b>); 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]⁺ (<b>2</b>) by pyridine or hexamethylphosphoramide (HMPA). These observations confirm the need for a shuttle base to form [(PN(H)P)PdH]⁺ (<b>2</b>) 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.