REACTIONS OF SC+, TI+, V+, FE+, CO+ AND NI+ WITH 1-FLUORONAPHTHALENE IN THE GAS-PHASE - METAL-CATALYZED OLIGOMER FORMATION AND OBSERVATION OF UNUSUAL RING FRAGMENTATION

Poly(naphthalyne) is of interest, in particular, due to its intrinsic electrical conductivity. Reported here are the initial steps in the metal-catalyzed polymerization of naphthalene as observed in the gas-phase reactions of Sc+, Ti+, V+, Fe+, Co+, and Ni+ with 1-fluoronaphthalene studied in a Fourier-transform mass spectrometer. Sc+, Ti+, V+, and Fe+ were found to dehydrofluorinate in a sequential fashion up to three neutral fluoronaphthalene molecules to form ions of the form MC10H6+, MC20H12+ and MC30H18+, where M represents the metal. Sc+ showed unusual reactivity by also being able to eliminate C2H2 from fluoronaphthalene, and Ti+ was found to eliminate a hydrogen atom to form TiC10H6F+. Second- and higher-order reactions were studied and several ionic products from primary and secondary reactions were investigated by collision-induced dissociation. Formation of unmetallated ions was also observed. For example, C20H12+ was determined to arise from MFC20H12+, for M = Ti, V, while for iron it was formed directly from FeC10H6+ in its reaction with the neutral fluoronaphthalene. This is in contrast with the behavior expected from an earlier study of fluorobenzene, where it was observed that (C6H4)n+ species arose from M(C6H4)n+ species.