Reactions of organonitrogen molecules with nickel(100)

Abstract

The adsorption and reaction of a variety of organonitrogen compounds on a Ni(100) surface have been examined with temperature-programmed reaction. Auger electron spectroscopy, and infrared spectroscopy. Monomethylamine adsorbs via the nitrogen lone pair of electrons and then undergoes C-N bond scission yielding adsorbed carbon, dihydrogen, and ammonia. Aniline ..pi..-bonds to the surface and polymerizes to form a thermally stable poly(aniline) surface film. Pyridine undergoes a temperature-induced orientational transformation. At low temperatures pyridine adsorbs with its ring parallel to the surface. At higher temperatures it appears to form an ..cap alpha..-pyridyl species with an activation barrier of 85 kJ/mol. Methyl groups on 2,6-lutidine sterically hinder this reaction. Methyl groups on 3,5-lutidine stabilize bonding via the nitrogen lone pair of electrons. The methyl groups on 3,5-lutidine increase electrophilic addition activity relative to pyridine and lead to polymerization of 3,5-lutidine, forming a thermally stable polymer film. Pyrimidine reacted in almost identical fashion to pyridine, suggesting that increased nucleophilic activity had little effect on the reaction behavior of heterocyclic compounds and that electrophilic reactions predominate.