Thermochemistry of N−N Containing Ions:  A Threshold Photoelectron Photoion Coincidence Spectroscopy Study of Ionized Methyl- and Tetramethylhydrazine

The unimolecular dissociation reactions of the methylhydrazine (MH) and tetramethylhydrazine (TMH) radical cations have been investigated using tandem mass spectrometry and threshold photoelectron photoion coincidence spectroscopy in the photon energy ranges 9.60−31.95 eV (for the MH ion) and 7.74−29.94 eV (for the TMH ion). Methylhydrazine ions (CH<sub>3</sub>NHNH<sub>2</sub><sup>+•</sup>) have three low-energy dissociation channels:  hydrogen atom loss to form CH<sub>2</sub>NHNH<sub>2</sub><sup>+</sup> (<i>m</i>/<i>z</i> 45), loss of a methyl radical to form NHNH<sub>2</sub><sup>+</sup> (<i>m</i>/<i>z</i> 31), and loss of methane to form the fragment ion <i>m</i>/<i>z</i> 30, N<sub>2</sub>H<sub>2</sub><sup>+•</sup>. Tetramethylhydrazine ions only exhibit two dissociation reactions near threshold:  that of methyl radical loss to form (CH<sub>3</sub>)<sub>2</sub>NNCH<sub>3</sub><sup>+</sup> (<i>m</i>/<i>z</i> 73) and of methane loss to form the fragment ion <i>m</i>/<i>z</i> 72 with the empirical formula C<sub>3</sub>H<sub>8</sub>N<sub>2</sub><sup>+•</sup>. The experimental breakdown curves were modeled with Rice−Ramsperger−Kassel−Marcus theory, and it was found that, particularly for methyl radical loss, variational transition state theory was needed to obtain satisfactory fits to the data. The 0 K enthalpies of formation (Δ<sub>f</sub><i>H</i><sub>0</sub>) for all fragment ions (<i>m</i>/<i>z</i> 73, <i>m</i>/<i>z</i> 72, <i>m</i>/<i>z</i> 45, <i>m</i>/<i>z</i> 31, and <i>m</i>/<i>z</i> 30) have been determined from the 0 K activation energies (<i>E</i><sub>0</sub>) obtained from the fitting procedure:  Δ<sub>f</sub><i>H</i><sub>0</sub>[(CH<sub>3</sub>)<sub>2</sub>NNCH<sub>3</sub><sup>+</sup>] = 833 ± 5 kJ mol<sup>-1</sup>, Δ<sub>f</sub><i>H</i><sub>0</sub> [C<sub>3</sub>H<sub>8</sub>N<sub>2</sub><sup>+•</sup>] = 1064 ± 5 kJ mol<sup>-1</sup>, Δ<sub>f</sub><i>H</i><sub>0</sub>[CH<sub>2</sub>NHNH<sub>2</sub><sup>+</sup>] = 862 ± 5 kJ mol<sup>-1</sup>, Δ<sub>f</sub><i>H</i><sub>0</sub>[NHNH<sub>2</sub><sup>+</sup>] = 959 ± 5 kJ mol<sup>-1</sup>, and Δ<sub>f</sub><i>H</i><sub>0</sub>[N<sub>2</sub>H<sub>2</sub><sup>+•</sup>] = 1155 ± 5 kJ mol<sup>-1</sup>. The breakdown curves have been measured from threshold up to <i>h</i>ν ≈ 32 eV for both hydrazine ions. As the photon energy increases, other dissociation products are observed and their appearance energies are reported.