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Infrared and DFT Investigations of the XC⋮ReX3 and HC⋮ReX3 Complexes: Jahn−Teller Distortion and the Methylidyne C−X(H) Stretching Absorptions
journal contribution
posted on 2007-10-15, 00:00 authored by Jonathan T. Lyon, Han-Gook Cho, Lester Andrews, Han-Shi Hu, Jun LiThe XC⋮ReX3 complexes (X = F, Cl) are produced by CX4 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-1, and the C−H stretching modes for HC⋮ReX3 at 3104 and 3097 cm-1,
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⋮ReX3 and HC⋮ReX3 complexes gives rise to distorted structures with Cs symmetry
and two equivalent longer Re−X bonds and one slightly shorter Re−X bond.