STEREOELECTRONIC EFFECTS ON HETEROATOMIC CHEMISTRY

采用双环和多环结构，可以控制

Employing bicyclic and polycyclic structures, it is possible to control bond rotations to enforce low nitrogen lone pair, lone pair interactions in chains of saturated nitrogens, and also to slow down proton transfer reactions in bond-cleaved intermediates. Using the principles, we will try to synthesize the first long-lived examples (of R2NN(R)Cl, R2NN(R)NR2, R2NN(R)N(R)NR2, RON(R)N(R)OR, and RSN(R)N(R)SR, as well as to study decomposition reactions of cations of these compounds and R2NOR-prime and R2NSR-prime. This work will make available new compounds with unprecidented functional groups which are easily oxidized; they may well prove biologically active. Tricyclic hexaalkylhydrazine dications of special structures chosen to make the neutral NN cleaved compounds exist in structures with large through-space NN interactions, yet have room for reagents to approach the nitrogen lone pairs will be prepared, and their redox chemistry studied. We are hoping to develop systems in which both the neutral and NN-cleaved dicationic forms with an NN bond will give the same 3e-sigma bonded intermediate. The neutral forms of these compounds will have strong through-space lone pair, lone pair interaction, which is destabilizing, and also will allow reagents to approach the lone pairs. We will study complexation of electrophiles such as protons and metal atoms by these compounds, looking for special selectivities in complexation. Electron-transfer of cyclic hydrazine cation radicals with the neutral hydrazine appears to generate unstable forms of certain hydrazines, which are not available by other methods. Study of the reactivity of these electronically and sterically destabilized conformational isomers will be pursued.