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

Palladium­(II) acetate (1) and two new complexes of the ligand α,α,α′,α′-tetramethyl-1,3-benzenedipropionate (esp2–), C s -Pd3(esp)3 ( C s -2) and C 3h -Pd3(esp)3 ( C 3h -2), are studied in the solid state and in solution. Variable-temperature NMR and DFT studies of C s -2 reveal an unusual shieldin...

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Published in:Inorganic chemistry 2018-07, Vol.57 (14), p.8046-8049
Main Authors: Pakula, Ryan J, Srebro-Hooper, Monika, Fry, Charles G, Reich, Hans J, Autschbach, Jochen, Berry, John F
Format: Article
Language:English
Subjects:
Chemistry
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Summary:Palladium­(II) acetate (1) and two new complexes of the ligand α,α,α′,α′-tetramethyl-1,3-benzenedipropionate (esp2–), C s -Pd3(esp)3 ( C s -2) and C 3h -Pd3(esp)3 ( C 3h -2), are studied in the solid state and in solution. Variable-temperature NMR and DFT studies of C s -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 Pd3 5+ species with a valence-trapped PdII–PdII–PdI electronic structure.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.8b01369