10.1021/ic701014u.s002
Jonathan T. Lyon
Jonathan T.
Lyon
Han-Gook Cho
Han-Gook
Cho
Lester Andrews
Lester
Andrews
Han-Shi Hu
Han-Shi
Hu
Jun Li
Jun
Li
Infrared and DFT Investigations of the XC⋮ReX<sub>3</sub> and HC⋮ReX<sub>3</sub>
Complexes: Jahn−Teller Distortion and the Methylidyne C−X(H)
Stretching Absorptions
American Chemical Society
2007
CX 4 reaction
absorption
carbon hybridization
argon matrix
Re
DFT Investigations
mode
bond
HC
Cs symmetry
cm
Jahn
vibrational frequencies
XC
frequency
complex
2007-10-15 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Infrared_and_DFT_Investigations_of_the_XC_ReX_sub_3_sub_and_HC_ReX_sub_3_sub_Complexes_Jahn_Teller_Distortion_and_the_Methylidyne_C_X_H_Stretching_Absorptions/2980807
The XC⋮ReX<sub>3</sub> complexes (X = F, Cl) are produced by CX<sub>4</sub> reaction with laser-ablated Re atoms, following oxidative
C−X insertion and α-halogen migration in favor of the carbon−metal triple bond and are identified through the
observation of characteristic absorptions in the argon matrix infrared spectra and comparison with vibrational
frequencies calculated by density functional theory. The methylidyne C−F and C−Cl stretching absorptions are
observed near 1584 and 1328 cm<sup>-1</sup>, and the C−H stretching modes for HC⋮ReX<sub>3</sub> at 3104 and 3097 cm<sup>-1</sup>,
respectively, which are substantially higher than the precursor stretching modes and in agreement with the general
trend that higher s-orbital character in carbon hybridization leads to a higher stretching frequency. The Jahn−Teller
effect in the doublet-state XC⋮ReX<sub>3</sub> and HC⋮ReX<sub>3</sub> complexes gives rise to distorted structures with <i>C</i><i><sub>s</sub></i> symmetry
and two equivalent longer Re−X bonds and one slightly shorter Re−X bond.