77903-37-8Relevant academic research and scientific papers
Extremely Congested Hydrazine Radical Cations
Nelsen, Stephen F.,Parmelee, William P.
, p. 3453 - 3456 (1981)
Addition of tert-butyllithium to the N2 tert-butylated diazenium cations derived from bicyclic azo compounds gave 2,3-di-tert-butyl-2,3-diazabicycloheptane (6), its 7,7-spirocyclopropyl analogue (9), and its bicyclooctane analogue (10).These very hindered tetraalkylhydrazines are unusually sensitive to both air and heat, and their radical cations decompose thermally at 25 deg C with rate constants of approximately 1, 0.1, and 10 s-1, respectively, undergoing de-tert-butylation.Despite their kinetic instability, these radical cations are thermodynamically slightly easier to form by one-electron removal from the neutral hydrazine than are analogues with the tert-butyl groups replaced by methyl groups.Destabilization of the neutral form by the bulky tert-butyl substituents almost exactly balances destabilization of the radical cationic form, leading to very small changes in E0' as the size of alkyl groups is increased.
