Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand

0532543 - ÚFCH JH 2022 RIV DE eng J - Článek v odborném periodiku
Ehret, F. - Filippou, V. - Blickle, S. - Bubrin, M. - Záliš, Stanislav - Kaim, W.
Structural and Oxidation State Alternatives in Platinum and Palladium Complexes of a Redox-Active Amidinato Ligand.
Chemistry - A European Journal. Roč. 27, č. 10 (2021), s. 3374-3381. ISSN 0947-6539. E-ISSN 1521-3765
Institucionální podpora: RVO:61388955
Klíčová slova: electron transfer * oxidation states * radical ligands
Obor OECD: Physical chemistry
Impakt faktor: 5.020, rok: 2021
Způsob publikování: Open access

Reaction of [Pt(DMSO)(2)Cl-2] or [Pd(MeCN)(2)Cl-2] 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)(2)C6H3}(4)] single crystals. Experimental and computational investigations were directed at the elucidation of the electronic structures, establishing the correct oxidation states within the alternatives [Pt-II(L-)(2)] or [Pt-.(L )(2)], [Pt-II(L0.5-)(2)](+) or [Pt-III(L-)(2)](+), [(Pd-II)(2)(mu-L-)(4)] or [(Pd-1.5)(2)(mu-L0.75-)(4)], and [(Pd-2.5)(2)(mu-L-)(4)](+) or [(Pd-II)(2)(mu-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)degrees in contrast to [Pd2L4], and the dimetal (Pd-2(4+)-> Pd-2(5+)) instead of ligand (L--> L ) oxidation of the dinuclear palladium compound.
Trvalý link: http://hdl.handle.net/11104/0311003