Structural Determination of NiCnH2n+ Ions in the Gas Phase Using Furier Transform Mass Spectrometry Collision-Induced Dissociation

Article abstract of DOI:10.1021/ja00342a011

In this paper we apply Fourier transform mass spectrometry to study the structures of NiCnH2n⁺ complexes generated from reactions of Ni⁺ with a variety of hydrocarbons and demonstrate that different isomeric structures can readily be distinguished both by a collision-induced dissociation and by specific ion-molecule reactions.Evidence is provided for four unique structures of NiC4H8⁺ generated from reactions of Ni+ with butane, hexane, 2,2-dimethylpropane, and cyclopentanone.Dehydrogenation reactions of Ni⁺ with n-alkanes yielded bis(olefin) complexes that are distinguishable from their isomeric monoalkane complexes.Ni⁺ is found to be highly selective for cleaving internal bonds and highly selective against insertion into terminal C-C bonds.Dehydrogenation becomes more competitive with alkane elimination when β-hydride transfer from secondary carbons are involved instead of from primary carbons.