title: Infrared spectra of CH3-MH through methane activation by laser-ablated Sn, Pb, Sb, and Bi atoms.
abstract: Methane activation has been carried out by laser-ablated Sn, Pb, Sb, and Bi atoms. All four metals generate the insertion complex (CH(3)-MH), but subsequent H-migration from C to M to form CH(2)-MH(2) and CH-MH(3) complexes is not observed. Our previous and present experimental and computational results indicate that the higher oxidation state complexes become less favored with increasing atomic mass in groups 14 and 15, which is opposite the general trend found for transition metals. The C-H bond insertion evidently occurs during reaction on sample condensation, and the product dissociates on broad-band photolysis afterward. The insertion complex contains a near right angle C-M-H moiety because of high p contribution from the metal center to the C-M and M-H bonds unlike many transition-metal analogues. The computed methylidene structures for these main group metals are not agostic possibly because of the absence of valence d-orbitals.
authors: Department of Chemistry, University of Incheon, 119 Academy-ro, Yonsu-gu, Incheon, 406-772, South Korea.
authors: Han-Gook
authors: HG
authors: Cho
authors: Lester
authors: L
authors: Andrews