Vibrational spectroscopy and theory of Fe(+)(CH(4))(n) (n = 1-4).

Vibrational spectra are measured for Fe(+)(CH(4))(n) (n = 1-4) in the C-H stretching region (2500-3200 cm(-1)) using photofragment spectroscopy. Spectra are obtained by monitoring CH(4) fragment loss following absorption of one photon (for n = 3, 4) or sequential absorption of multiple photons (for n = 1, 2). The spectra have a band near the position of the antisymmetric C-H stretch in isolated methane (3019 cm(-1)), along with bands extending >250 cm(-1) to the red of the symmetric C-H stretch in methane (2917 cm(-1)). The spectra are sensitive to the ligand configuration (η(2) vs η(3)) and to the Fe-C distance. Hybrid density functional theory calculations are used to identify possible structures and predict their vibrational spectra. The IR photodissociation spectrum shows that the Fe(+)(CH(4)) complex is a quartet, with an η(3) configuration. There is also a small contribution to the spectrum from the metastable sextet η(3) complex. The Fe(+)(CH(4))(2) complex is also a quartet with both CH(4) in an η(3) configuration. For the larger clusters, the configuration switches from η(3) to η(2). In Fe(+)(CH(4))(3), the methane ligands are not equivalent. Rather, there is one short and two long Fe-C bonds, and each methane is bound to the metal in an η(2) configuration. For Fe(+)(CH(4))(4), the calculations predict three low-lying structures, all with η(2) binding of methane and very similar Fe-C bond lengths. No single structure reproduces the observed spectrum. The approximately tetrahedral C(1) ((4)A) structure contributes to the spectrum; the nearly square-planar D(2d) ((4)B(2)) and the approximately tetrahedral C(2) ((4)A) structure may contribute as well.