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Low‐Temperature Isolation of a Labile Silylated Hydrazinium‐yl Radical Cation, [(Me 3 Si) 2 N−N(H)SiMe 3 ] .+
Author(s) -
Reiß Fabian,
Villinger Alexander,
Brand Harald,
Baumann Wolfgang,
Hollmann Dirk,
Schulz Axel
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200854
Subject(s) - chemistry , hydrazine (antidepressant) , radical ion , raman spectroscopy , electron paramagnetic resonance , crystallography , radical , hydrate , bond length , decomposition , medicinal chemistry , ion , inorganic chemistry , crystal structure , organic chemistry , nuclear magnetic resonance , physics , chromatography , optics
The oxidation of silylated hydrazine, (Me 3 Si) 2 N−N(H)SiMe 3 , with silver salts led to the formation of a highly labile hydrazinium‐yl radical cation, [(Me 3 Si) 2 N−N(H)SiMe 3 ] .+ , at very low temperatures (decomposition > −40 °C). EPR, NMR, DFT and Raman studies revealed the formation of a nitrogen‐centered radical cation along the N−N unit of the hydrazine. In the presence of the weakly coordinating anion [Al{OCH(CF 3 ) 2 } 4 ] − , crystallization and structural characterization in the solid state were achieved. The hydrazinium‐yl radical cation has a significantly shortened N−N bond and a nearly planar N 2 Si 3 framework, in contrast to the starting material. According to DFT calculations, the shortened N−N bond has a total bond order of 1.5 with a π‐bond order of 0.5. The π bond can be regarded as a three‐π‐electron, two‐center bond.