Electron paramagnetic resonance spectroscopic study of radical cations from hydrazine, methylhydrazine, and dimethylhydrazines
The substrates hydrazine, methylhydrazine, 1,1-dimethylhydrazine, and 1,2-dimethylhydrazine have been investigated in turn within an aqueous continuous-flow system at 25 ± 2° using the titanous chloride-hydrogen peroxide radical-generating method. For each hydrazine the electron paramagnetic resonance spectrum of the corresponding monopositive radical ion was the only one observed, viz. [NH2NH2]·+, [CH3NHNH2]·+, [(CH3)2NNH2]·+, [cis-CH3NHNHCH3]·+, and [trans-CH3NHNHCH3]·+. The hydrogen and nitrogen nuclear hyperfine coupling constants of these radical cations have been determined and discussed in terms of the σ-π interaction theories of Karplus and Fraenkel and McConnell. Values for several empirically calculated spin-polarization parameters are presented.
Smith, P; Stevens, RD; Kaba, RA
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