Electronic structures of organometallic complexes of f elements LXXXII: Comparison of assigned experimental and calculated (on the basis of density functional theory) frequencies of normal vibrations of the first homoleptic organometallic complex of the lanthanides: Tris(η5-tetramethylcyclopentadienyl)lanthanum

The far and mid infrared spectra of powdered La(eta(5)-C5Me4H)(3) as well as polarized Raman spectra of an oriented single crystal (where the principal axes of the two molecules per unit cell are uniformly oriented) have been recorded. Applying the selection rules of C-3h symmetry to the experimental data, numerous signals were assigned which agree well with the predictions of a calculation based on density functional theory. Neglecting nu C-H and gamma Cp-H (out of plane) modes, an r.m.s. deviation of 21.9 cm(-1) for 71 assignments was achieved. Skeletal and intra-ligand vibrations were separated and an inspection of the vibronic sidebands of the purely electronic hypersensitive absorption transitions I-4(9/2) -> (4)G(5/2) of Nd(eta(5)-(C5MeH)-H-4)(3) showed that mainly the latter are coupled. (C) 2014 Elsevier B.V. All rights reserved.