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

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, U...

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Published in:Chemistry : a European journal Vol. 27; no. 10; pp. 3374 - 3381
Main Authors: Ehret, Fabian, Filippou, Vasileios, Blickle, Svenja, Bubrin, Martina, Záliš, Stanislav, Kaim, Wolfgang
Format: Journal Article
Language:English
Published: WEINHEIM Wiley 15.02.2021
Wiley Subscription Services, Inc
John Wiley and Sons Inc
Subjects:
Cations
Chemistry
Chemistry, Multidisciplinary
Computer applications
Crystal structure
Crystals
Electrochemistry
electron transfer
Ligands
Magnetic resonance
Oxidation
oxidation states
Palladium
Palladium compounds
Physical Sciences
Platinum
radical ligands
Science & Technology
Single crystals
spectroelectrochemistry
Spectroscopy
spin distribution
Valence
oxidation states
ORDER
ELECTRON
MONONUCLEAR
electron transfer
APPROXIMATION
spin distribution
spectroelectrochemistry
REACTIVITY
radical ligands
METAL
ISSN:0947-6539, 1521-3765, 1521-3765
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Summary: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. Qualitatively different structures and electron transfer behavior have been established for platinum and palladium complexes [PtL2]0/+ and [Pd2L4]0/+ with a redox‐active amidinato ligand L−/L..
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.202003636