Electronic structures of organometallic complexes of f elements LXXIV: First Raman spectroscopic polarization measurements on uniformly oriented sandwich complex molecules: Bis(η5-pentamethylcyclopentadienyl)ruthenium

Electronic structures of organometallic complexes of f elements LXXV

“…The inner-ligand vibrational spectra of LnCp * 3 compounds have not been analyzed up to now, thus no closer assignments of the nature of the coupling vibrations can be given. However, in the case of oriented RuCp * 2 single crystals, the polarized Raman spectra exhibit signals at 950 and 1166 cm À1 , the polarizations of which are compatible with e 2 and e 2 symmetry [1] (assuming a simple model of local C 5v symmetry). A band near 1405 cm À1 was not detected, but four neighboring ones at 1362, 1367, 1381 and 1421 cm À1 of e 2 , e 1 , e 2 and a 1 /e 1 symmetry appeared [1] (see Table 6).…”

“…However, in the case of oriented RuCp * 2 single crystals, the polarized Raman spectra exhibit signals at 950 and 1166 cm À1 , the polarizations of which are compatible with e 2 and e 2 symmetry [1] (assuming a simple model of local C 5v symmetry). A band near 1405 cm À1 was not detected, but four neighboring ones at 1362, 1367, 1381 and 1421 cm À1 of e 2 , e 1 , e 2 and a 1 /e 1 symmetry appeared [1] (see Table 6). OsCp * 2 shows inner-ligand vibrational levels at nearly the same energies as RuCp * 2 [44] but assignments were given to both irreducible representations and normal modes n i s (see Table 6).…”

“…1(b)). Obviously, these additional signals are due to polarization leaks, vibronic sidebands, weak luminescence transitions initiating at levels of the multiplet 4 F 5/2 (vide infra) and inner-ligand vibrations of the Cp * ring [1].…”

Electronic structures of organometallic complexes of f elements LXXVII: Complementary information of polarized Raman spectra of oriented single crystals and model calculations on the basis of density functional theory for assigning the vibrational spectra of decamethylferrocene

“…On the basis of the polarized Raman spectra of an oriented monoclinic single crystal of RuCp* 2 (Cp* ¼ h 5 eC 5 Me 5 ), reliable assignments of Raman active normal modes could be achieved [1,15] (the fivefold molecular axes of the two eclipsed RuCp* 2 molecules per unit cell are aligned [16]). Since the results for frequencies and relative intensities of DFT calculations agreed well in the case of the Raman active normal modes [1,15], the IR active ones were also assigned on the basis of these DFT calculations [1].…”

“…Since the results for frequencies and relative intensities of DFT calculations agreed well in the case of the Raman active normal modes [1,15], the IR active ones were also assigned on the basis of these DFT calculations [1].…”