GAS-PHASE CHEMISTRY OF BARE TRANSITION-METAL IONS IN COMPARISON .2. REACTIONS OF TI+ TO ZN+ WITH 2-ETHYLBUTANENITRILE

The reactions of the first-row transition-metal ions from Ti+ to Zn+ with 2-ethylbutanenitrile (23) are studied using a Fourier transform ion cyclotron resonance (FTICR) spectrometer. The general behavior of the ions is compared and is found to be in line with previous studies. While the early-transition-metal ions Ti+ and V+ mainly give rise to C-H activation products, Cr+, Mn+, and Zn+ are unreactive without collisional activation and form only adduct complexes. For Fe+-Cu+ three processes are operative whose relative importance varies: an ion/dipole mechanism which leads to MHCN+ ions and loss of HCN, remote functionalization forming H-2 and C2H4 from the chain termini, and an allylic mechanism which generates CH4 by initial C-CN insertion. The results are further compared with those of the lower homologue, 2-methylbutanenitrile, studied in part 1, and are found to be in very good agreement. Finally, an instrumental comparison is provided between ion/molecule reactions of Fe+ with 23 under FTICR conditions and metastable-ion decompositions of Fe(23)+ adduct complexes in a sector mass spectrometer showing that the two approaches provide the same results within previously formulated restrictions.