Showing papers by "Hans J. Reich published in 2018"

Palladium Acetate Revisited: Unusual Ring-Current Effects, One-Electron Reduction, and Metal-Metal Bonding.

Abstract: Palladium(II) acetate (1) and two new complexes of the ligand α,α,α′,α′-tetramethyl-1,3-benzenedipropionate (esp2–), Cs-Pd3(esp)3 (Cs-2) and C3h-Pd3(esp)3 (C3h-2), are studied in the solid state and in solution. Variable-temperature NMR and DFT studies of Cs-2 reveal an unusual shielding region above the Pd atoms. The compounds show a surprising quasi-reversible reduction between −880 and −1200 mV versus Fc/Fc+, and the Pd3(esp)3 complexes may be cleanly reduced electrochemically. EPR spectra of reduced samples show pseudo-axial signals with 105Pd hyperfine coupling, consistent with unprecedented, isostructural Pd35+ species with a valence-trapped PdII–PdII–PdI electronic structure.