Infrared Spectra of CH<sub>3</sub>–MH through
Methane Activation by Laser-Ablated Sn, Pb, Sb, and Bi Atoms
Han-Gook Cho
Lester Andrews
10.1021/jp305117d.s001
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
Methane activation has been carried out by laser-ablated
Sn, Pb,
Sb, and Bi atoms. All four metals generate the insertion complex (CH<sub>3</sub>–MH), but subsequent H-migration from C to M to form
CH<sub>2</sub>–MH<sub>2</sub> and CH–MH<sub>3</sub> 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.
2012-08-23 00:00:00
Pb
Infrared Spectra
insertion
oxidation state complexes
group metals
Bi atoms
Methane Activation
Bi AtomsMethane activation
groups 14
CH
Sn
Sb
sample condensation
p contribution
methylidene structures
transition metals
metal center
bond