Synthesis, Structure, and Conformational Dynamics of Bridgehead-Substituted Nitrosamines. Di-1-adamantylnitrosamine...

The synthesis of two bridgehead-substituted nitrosamines, di-1-adamantylnitrosamine (1) and di-1-norbornylnitrosamine (2), is described, and their solid state crystal structures are reported. Large bridgehead substituents increase the NNO angle of the nitrosamine (compared to that found for dimethylnitrosamine) without deconjugating the NNO pi system significantly. This structural change correlates with a red-shifted optical absorption, a diminished N,N rotational barrier, and a greater ease of oxidation of these hindered nitrosamines than is observed for dimethylnitrosamine. The electronic basis of these structure/function correlations is examined. It is concluded that 1 is more strained than N-nitroso-2,2,6,6-tetramethylpiperidine (3) which is more strained than 2 and that a raised (in energy) NO n orbital is primarily responsible for the extreme properties of the former.