ION MOLECULE REACTIONS OF TRANSITION-METAL IONS WITH NITRILES IN THE GAS-PHASE - COMPETITIVE FORMATION OF BOTH END-ON AND SIDE-ON COORDINATION

First field-free region B/E linked scan studies of metastable and particularly collision-induced dissociations show that two competitive coordination processes (''end-on'' and ''side-on'') exist in the complexation of metal ions (Ni+, Co+, Fe+, and Mn+) with alkanenitriles in the FAB source of an E/B configuration mass spectrometer. Analysis of the B/E linked scan CA spectra gives approximate percentages of the end-on coordination mode in the reactive complexes. An unusual beta-methyl migration, involved in the elimination of CH4 from end-on complexes. may be in competition with beta-H migration/elimination of H-2 and beta-C-C bond cleavage/elimination of alkene. For the side-on complexes, the metal ions can insert into various C-C bonds followed by beta-H transfer/competitive elimination of alkene and alkane or by a direct C-M+ bond cleavage to give an alkyl