%0 Journal Article %1 Ehret.2021 %A Ehret, Fabian %A Filippou, Vasileios %A Blickle, Svenja %A Bubrin, Martina %A Zalis, Stanislav %A Kaim, Wolfgang %D 2021 %J Chemistry - A European Journal %K imported %N 10 %P 3374-3381 %R 10.1002/chem.202003636 %T Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand %V 27 %X 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, electrochem., 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][B3,5-(CF3)2C6H34] single crystals. Exptl. 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(m-L-)4] or [(Pd1.5)2(m-L0.75-)4], and [(Pd2.5)2(m-L-)4]+ or [(PdII)2(m-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+$\rightarrow$Pd25+) instead of ligand (L-$\rightarrow$L) oxidation of the dinuclear palladium compound

@article{Ehret.2021, abstract = {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, electrochem., 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. Exptl. 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(\textgreek{m}-L-)4] or [(Pd1.5)2(\textgreek{m}-L0.75-)4], and [(Pd2.5)2(\textgreek{m}-L-)4]+ or [(PdII)2(\textgreek{m}-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+$\rightarrow$Pd25+) instead of ligand (L-$\rightarrow$L) oxidation of the dinuclear palladium compound}, added-at = {2022-06-15T12:05:25.000+0200}, author = {Ehret, Fabian and Filippou, Vasileios and Blickle, Svenja and Bubrin, Martina and Zalis, Stanislav and Kaim, Wolfgang}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2eb800504d63bb48ffd306d3290d6b393/huebleriac}, doi = {10.1002/chem.202003636}, interhash = {2439f78083f949cabf04da8da65ffae0}, intrahash = {eb800504d63bb48ffd306d3290d6b393}, issn = {0947-6539}, journal = {Chemistry - A European Journal}, keywords = {imported}, number = 10, pages = {3374-3381}, timestamp = {2022-06-15T10:05:25.000+0200}, title = {Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand}, volume = 27, year = 2021 }