Matrix infrared spectroscopic studies of the MH-C2H3 and MH2-C2H2 intermediates in the reactions of ethylene with laser-ablated group 5 metal atoms.
Reactions of ethylene with laser-ablated group 5 metal atoms in excess argon have been carried out during codeposition at 8 K, and the matrix infrared spectra of intermediate products have been investigated. Oxidative C-H insertion of the transition metal into a C-H bond occurs and beta-hydrogen transfer follows to form the dihydrido complexes (MH2-C2H2). In the Ta spectra, the dihydrido complex is the primary product, whereas the Nb and V spectra reveal absorptions from both the insertion (MH-C2H3) and dihydrido complexes. The insertion and dihydrido complexes identified here are in fact the reaction intermediates in the hydrogen elimination of ethylene proposed in previous reaction dynamics studies. Calculations also show that the higher oxidation-state complex becomes more stable relative to the insertion product going down the group 5 family.
Cho
Han-Gook
HG
Department of Chemistry, University of Incheon, 177 Dohwa-dong, Nam-ku, Incheon, 402-749, South Korea.
Andrews
Lester
L