The Hydrazyl Cation

Formation. N2H3 ions were observed as secondary ions in the mass spectrum of gaseous ammonia (electron energies up to 80 V, NH3 pressures of 2.5x10 to 65x10 Torr). The ions were presumably formed by the reactions NH + NH3-NHj + NH3-+N2H3 + H2 (cross sections cr = 35x 10 and 5.3x 10 cm spectively) [1]. 

Calculated with ab initio methods (G2 procedure) [10]. calculated value [11]. 

N2H3 ions were formed by interaction of N2H4 with a platinum surface. The yield of N2H3 ions was monitored with a field ion mass spectrometer in the range of 298 to 448 K, passing through a maximum at 335 K [12]. 

The formation of N2H3 ions was assumed to be the rate-determining first step in the electrooxidation of hydrazine at a dropping mercury electrode according to N2H4 + OH - N2Hj + H20 + 2e [14]. 

Structure and Properties. Ab initio [10,11,15 to 17] and semiempirical [11,18] calculations predicted a planar structure (Cg symmetry) for the N2HJ ion in its electronic ground state A. An ab initio SCF MO calculation at the 4-31G level [16] and SCF MO [11] and MP2 [10] calculations at the 6-31G level gave the following optimized geometry (bond distance r in A, angles a for atom numbering, see p. 75)  

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D. Kost, K. Aviram, and M. Raban, Structural molecular orbital analyses of the hydrazyl cation radicals and anion, J. Org. Chem., 54 (1989) 4903-4908. 

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