The chemistry of nickel on the edge of polycyclic aromatic hydrocarbons

Transition metals provide an unique opportunity to investigate the chemistry of Polycyclic aromatic carbon compounds (PACs). This paper focuses on the initial work necessary to establish an understanding of the chemistry of this class of compounds. Initial investigations have demonstrated the potential for expansion and functionalization of PACs by nickel. Zero valent nickel readily inserts into the carbon-halogen bond of PACs to yield an oxidative addition product. In particular, 1,8-dibromonaphthalene reacts with a mixture of Ni(COD)2 and trimethylphosphine to form the oxidative addition product Ni(PMe2)2(Br)(C10H6Br). It is further possible to carry out a reduction of this product with Na/Hg to form perylene or, in the presence of an alkyne, form the 1,2-disubstituted acenaphthylene. The results show promise for the further development of larger PACs using the techniques that have been explored, and the potential for their development will be discussed. (Abstract shortened by UMI.).