التفاصيل البيبلوغرافية
| العنوان: |
Ligand-Centered Triplet Diradical Supported by a Binuclear Palladium(II) Dipyrrindione |
| المؤلفون: |
Clayton J. Curtis (11231488), Andrei V. Astashkin (1324170), Jeanet Conradie (734755), Abhik Ghosh (653725), Elisa Tomat (1327788) |
| سنة النشر: |
2021 |
| المجموعة: |
Smithsonian Institution: Digital Repository |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Cell Biology, Environmental Sciences not elsewhere classified, Biological Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Information Systems not elsewhere classified, quasi-reversible ligand-centered re., bidentate dipyrrindiones, electron reservoirs, dianionic species, divalent palladium centers, oligopyrrolic π systems, dipyrrindione ligands, Q-band EPR spectroscopic experiments, transition-metal complexes, cobaltocenium salt features, redox-active ligands, one-electron redox chemistry, two-electron chemical reduction, DFT, deprotonation-driven dimerization, hydroxo bridges, macrocyclic ligands, triplet state, Ligand-Centered Triplet Diradical, EPR temperature dependence |
| الوصف: |
Oligopyrroles form a versatile class of redox-active ligands and electron reservoirs. Although the stabilization of radicals within oligopyrrolic π systems is more common for macrocyclic ligands, bidentate dipyrrindiones are emerging as compact platforms for one-electron redox chemistry in transition-metal complexes. We report the synthesis of a bis(aqua) palladium(II) dipyrrindione complex and its deprotonation-driven dimerization to form a hydroxo-bridged binuclear complex in the presence of water or triethylamine. Electrochemical, spectroelectrochemical, and computational analyses of the binuclear complex indicate the accessibility of two quasi-reversible ligand-centered reduction processes. The product of a two-electron chemical reduction by cobaltocene was isolated and characterized. In the solid state, this cobaltocenium salt features a folded dianionic complex that maintains the hydroxo bridges between the divalent palladium centers. X-band and Q-band EPR spectroscopic experiments and DFT computational analysis allow assignment of the dianionic species as a diradical with spin density almost entirely located on the two dipyrrindione ligands. As established from the EPR temperature dependence, the associated exchange coupling is weak and antiferromagnetic ( J ≈ −2.5 K), which results in a predominantly triplet state at the temperatures at which the measurements have been performed. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Ligand-Centered_Triplet_Diradical_Supported_by_a_Binuclear_Palladium_II_Dipyrrindione/15106279 |
| DOI: |
10.1021/acs.inorgchem.1c01691.s001 |
| الاتاحة: |
https://doi.org/10.1021/acs.inorgchem.1c01691.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.2506DB95 |
| قاعدة البيانات: |
BASE |