Search

The HeI photoelectron spectra of the complexes η4-1-vinylnaphthalene–Fe(CO)3 and η4-2-vinylnaphthalene–Fe(CO)3 and the free organic ligands 1-vinylnaphthalene and 2-vinylnaphthalene are measured. The spectra are interpreted on the basis of quantum-chemical calculations by the density functional method in the SVWN/6-31G(d) local density approximation and with the B3LYP/6-31G(d) hybrid exchange-correlation functional. The Kohn–Sham orbital energies with calibration corrections are shown to reproduce well the vertical ionization potentials of both the irontricarbonyl π complexes under study and their ligands. The relative ionization cross sections σi of the valence orbitals of the complexes are calculated in terms of the Gelius model. These quantities prove to agree perfectly with the relative ionization cross sections σiexp determined experimentally from direct estimation of the band areas of the photoelectron spectra. © 2005 Pleiades Publishing, Inc. [ABSTRACT FROM AUTHOR]

The HeI and NeI photoelectron spectra of irontricarboniyl complexes with cyclic diene ligands—α-methylstyrene, orthoquinodimethane, and cyclooctatetraene—were obtained. The results of quantum-chemical calculations of the molecules of these compounds in the approximation of the density functional theory (B3LYP/6-31G*) are presented. It is shown that this approximation describes well the excited ionic states of the π complexes under study. The relative ionization cross sections σ[sub π] and σ[sub 3][sub d], which characterize the probability of removal of electrons from the molecular π-ligand and 3d-metal orbitals, are estimated. The mechanism of the selective coordination of the Fe(CO)[sub 3] groups to corresponding organic ligands is discussed. The energies of the L–Fe(CO)[sub 3] chemical bond are calculated. © 2004 MAIK “Nauka / Interperiodica”. [ABSTRACT FROM AUTHOR]