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

Abstract

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.

Electrocatalytic radical degradation of 2-aminoethanol by nickel, palladium and platinum complexes bearing non-innocent diarylamido/bis(phosphine) pincer ligand

“…Our research team has been focusing on the design, synthesis, and catalytic application of pincer-type complexes of group 10 metals during the past few years [29][30][31][32][33][34][35][36][37][38][39][40][41]. Recently, we have reported the electrochemical properties of bis[2-(di-i-propylphosphino)-4-methylphenyl]amido complexes [(PNP)MCl] of Ni (1), Pd (2) and Pt (3) (Fig.…”