biostudies-literatureEhret FMinisterium für Wissenschaft, Forschung und Kunst Baden-WürttembergDeutsche Forschungsgemeinschaft3374-3381https://www.ebi.ac.uk/biostudies/studies/S-EPMC7986709biostudies-literatureUnknown27(10)Reaction of [Pt(DMSO)2 Cl2 ] or [Pd(MeCN)2 Cl2 ] with the electron-rich LH=N,N'-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2 ] (1) but dinuclear [Pd2 L4 ] (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 [Pd2 L4 ]+ were also studied, the latter as [Pd2 L4 ][B{3,5-(CF3 )2 C6 H3 }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 [Pd2 L4 ], and the dimetal (Pd2 4+ →Pd2 5+ ) instead of ligand (L- →L ) oxidation of the dinuclear palladium compound.Chemistry (Weinheim an der Bergstrasse, Germany)Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand.PMC7986709INST 40/467-1 FUGG (Justus Cluster)bwHPCKaim WEhret FZalis SBlickle SFilippou VBubrin MfalseStructural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand.Reaction of [Pt(DMSO)2 Cl2 ] or [Pd(MeCN)2 Cl2 ] with the electron-rich LH=N,N'-bis(4-dimethylaminophenyl)ethanimidamide yielded mononuclear [PtL2 ] (1) but dinuclear [Pd2 L4 ] (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 [Pd2 L4 ]+ were also studied, the latter as [Pd2 L4 ][B{3,5-(CF3 )2 C6 H3 }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 [Pd2 L4 ], and the dimetal (Pd2 4+ →Pd2 5+ ) instead of ligand (L- →L ) oxidation of the dinuclear palladium compound.2021-01-01T00:00:00Z2021 Feb2025-04-04T14:35:10.859Z2025-04-04T14:35:10.859ZS-EPMC79867093295941510.1002/chem.202003636