%0 Journal Article
%A Cho, Han-Gook
%A Andrews, Lester
%D 2012
%T Infrared Spectra of CH3–MH through
Methane Activation by Laser-Ablated Sn, Pb, Sb, and Bi Atoms
%U https://acs.figshare.com/articles/journal_contribution/Infrared_Spectra_of_CH_sub_3_sub_MH_through_Methane_Activation_by_Laser_Ablated_Sn_Pb_Sb_and_Bi_Atoms/2493658
%R 10.1021/jp305117d.s001
%2 https://acs.figshare.com/ndownloader/files/4136521
%K Pb
%K Infrared Spectra
%K insertion
%K oxidation state complexes
%K group metals
%K Bi atoms
%K Methane Activation
%K Bi AtomsMethane activation
%K groups 14
%K CH
%K Sn
%K Sb
%K sample condensation
%K p contribution
%K methylidene structures
%K transition metals
%K metal center
%K bond
%X Methane activation has been carried out by laser-ablated
Sn, Pb,
Sb, and Bi atoms. All four metals generate the insertion complex (CH3–MH), but subsequent H-migration from C to M to form
CH2–MH2 and CH–MH3 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.
%I ACS Publications