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Oxidation State Assignments in the Organoplatinum One‐Electron Redox Series [(N ^ N)PtMes 2 ] n , n = +,0, –,2‐
Author(s) -
Bauer Sonja,
Záliš Stanislav,
Fiedler Jan,
Ringenberg Mark R.,
Kaim Wolfgang
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000257
Subject(s) - chemistry , electron paramagnetic resonance , redox , steric effects , crystallography , oxidation state , ligand (biochemistry) , electron transfer , radical , ketone , density functional theory , spectroscopy , photochemistry , medicinal chemistry , stereochemistry , inorganic chemistry , computational chemistry , metal , nuclear magnetic resonance , organic chemistry , quantum mechanics , biochemistry , physics , receptor
The neutral complexes [(N ^ N)PtMes 2 ], N ^ N = bis(1‐methyl‐2‐imidazolyl)ketone (bik) or N,N'‐disubstituted 1,2‐bis‐iminoacenaphthenes (R‐BIAN), Mes = mesityl, were obtained and characterized as Pt II species with planar N 2 PtC 2 configuration and charge transfer transitions in the visible. Reversible one‐electron reduction produces radical anion complexes with the spin predominantly localized in the N ^ N ligand, according to EPR, UV/Vis‐IR spectroelectrochemistry, DFT and TD‐DFT studies. Reversible one‐electron oxidation was also possible, attributed to the steric and electronic influence from the mesityl ligands. The EPR silent cation [(bik)PtMes 2 ] + was characterized by UV/Vis‐NIR spectroscopy and TD‐DFT calculations as a system with spin density contributions from Pt (31 %) and two mesityl groups (69 %).
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