Naphthalene proton sponges as hydride donors: diverse appearances of the tert-amino-effect.

It has been shown that the 1-NMe(2) group in the 2-substituted 1,8-bis(dimethylamino)naphthalenes (proton sponges) can intramolecularly donate a hydride ion to an appropriate electron-accepting ortho-substituent such as diarylcarbenium ion, β,β'-dicyanovinyl or methyleneiminium group. This produces the 1-N(+)(Me)=CH(2) functionality and triggers a number of further transformations (tert-amino effect) including peri-cyclization, ortho-cyclization or hydrolytic demethylation. In each particular case, the course of the reaction is determined by the nature of the ortho-substituent and the most potent nucleophile presenting in the reaction mixture.

Pi-donor BETS based bifunctional superconductor with polymeric dicyanamidomanganate(II) anion layer: kappa-(BETS)2Mn[N(CN)2]3.

Crystals of the bis(ethylenedithio)tetraselenafulvalene (BETS) radical cation salt with dicyanamidomanganate(II) anion, kappa-(BETS)2Mn[N(CN)2]3, were synthesized, which combine conducting and magnetic properties at ambient pressure and are superconducting (Tc approximately/= 5 K) at a moderate pressure of 0.3 kbar.

Conformational study of 2-arylazo-1-vinylpyrroles.

Conformational study of 2-phenylazo-1-vinylpyrrole and 2-(4-bromophenyl)azo-5-methyl-1-vinylpyrrole was performed on the basis of the experimental measurements and high-level ab initio calculations of their 13C--13C and 13C--1H spin-spin coupling constants, showing marked stereochemical behaviour upon the internal rotation of the vinyl group and the pyrrolyl moiety. In liquid phase, both compounds were found to adopt predominant s-trans-s-trans conformation with the noticeable population (ca. 30%) of the higher-energy s-cis-s-trans conformation in the latter compound.