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http://dx.doi.org/10.18419/opus-14357
Autor(en): | Ehret, Fabian Filippou, Vasileios Blickle, Svenja Bubrin, Martina Záliš, Stanislav Kaim, Wolfgang |
Titel: | Structural and oxidation state alternatives in platinum and palladium complexes of a redox‐active amidinato ligand |
Erscheinungsdatum: | 2021 |
Dokumentart: | Zeitschriftenartikel |
Seiten: | 3374-3381 |
Erschienen in: | Chemistry - a European journal 27 (2021), S. 3374-3381 |
URI: | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-143764 http://elib.uni-stuttgart.de/handle/11682/14376 http://dx.doi.org/10.18419/opus-14357 |
ISSN: | 1521-3765 0947-6539 |
Zusammenfassung: | Reaction of [Pt(DMSO)2Cl2] or [Pd(MeCN)2Cl2] with the electron‐rich LH=N,N’‐bis(4‐dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2] (1) but dinuclear [Pd2L4] (2), a paddle‐wheel complex. The neutral compounds were characterized through experiments (crystal structures, electrochemistry, UV‐vis‐NIR spectroscopy, magnetic resonance) and TD‐DFT calculations as metal(II) species with noninnocent ligands L-. The reversibly accessible cations [PtL2]+ and [Pd2L4]+ were also studied, the latter as [Pd2L4][B{3,5‐(CF3)2C6H3}4] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [PtII(L-)2] or [Pt.(L )2], [PtII(L0.5-)2]+ or [PtIII(L-)2]+, [(PdII)2(μ‐L−)4] or [(Pd1.5)2(μ‐L0.75-)4], and [(Pd2.5)2(μ‐L-)4]+ or [(PdII)2(μ‐L0.75-)4]+. In each case, the first alternative was shown to be most appropriate. Remarkable results include the preference of platinum for mononuclear planar [PtL2] with an N‐Pt‐N bite angle of 62.8(2)° in contrast to [Pd2L4], and the dimetal (Pd24+→Pd25+) instead of ligand (L-→L ) oxidation of the dinuclear palladium compound. |
Enthalten in den Sammlungen: | 03 Fakultät Chemie |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | |
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CHEM_CHEM202003636.pdf | 1,96 MB | Adobe PDF | Öffnen/Anzeigen |
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