Metal-cyclic hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and IR-UV resonant two-photon ionization (R2PI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the ZEKE measurements with density functional theory (DFT) calculations. In addition, C-H stretching frequencies were measured from the R2PI spectra. In this dissertation, metal complexes of 1, 3, 5, 7-cyclo-octatetraene (COT), toluene, p-xylene, mesitylene, hexamethylbenzene, biphenyl, naphthalene, pyrene, perylene, and coronene were studied. For each metal-ligand complex, different effects from the metal coordination have been identified. Although free COT is a nonaromatic molecule with a tub-shaped structure, the group III transition metal atoms (Sc, Y, and La) donate two electrons to a partially filled π orbital of COT, making the ligand a dianion. As a result, metal coordination converts COT into a planar, aromatic structure and the resulting complex exhibits a half-sandwich structure. For the Sc(methylbenzene) complexes, the benzene rings of the ligands are bent and the π electrons are localized in a 1, 4-diene fashion due to differential Sc binding with the carbon atoms of the rings. Due to differential metal binding, the degenerate d orbitals split and the Sc-methylbenzene complexes prefer the low-spin ground electronic states. In addition, as the number of methyl group substituents in the ligand increases, the ionization energies (IEs) of the Sc-methylbenzene complexes decrease. However, Ti, V, or Co coordination does not disrupt the delocalized π electron network within the carbon skeleton in the high-spin ground states of the metal complexes. For group VI metal (Cr, Mo, and W)-bis(toluene) complexes, methyl substitution on the benzene ring yields complexes with four rotational conformers of 0°, 60°, 120°, and 180° conformation angles between two methyl groups. In addition, variable-temperature ZEKE spectroscopy using He, Ar, or their mixtures has determined the totally eclipsed 0° rotamer to be the most stable. When there are two equivalent benzene rings, the metal (Ti, Zr or Hf) binds to both the benzene rings of biphenyl, or the metal (Li) binds to one of the benzene rings of naphthalene. On the other hand, the metal (Li) favors the ring-over binding site of the benzene ring with a higher π electron content and aromaticity in pyrene, perylene, and coronene.

Metal-hydrocarbon complexes were prepared in a laser-vaporization molecular beam source and studied by single-photon zero electron kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) spectroscopy. The ionization energies and vibrational frequencies of the metal complexes were measured from the ZEKE and MATI spectra. Metal-ligand bonding and low-lying electronic states of the neutral and ionized complexes were analyzed by combining the spectroscopic measurements with quantum chemical calculations and spectral simulations. In this dissertation, the metal complexes of mesitylene, aniline, cyclooctatetraene, benzene, ethene, and propene were studied. For each complex, different effects from metal coordination have been identified. Although metal-bis(mesitylene) sandwich complexes may adopt eclipsed and staggered conformations, the group VI metal-bis(mesitylene) complexes are determined to be in the eclipsed form. In this form, rotational conformers with the methyl group dihedral angles of 0 and 60° are identified for the Cr complex, whereas the 0° rotamer is observed for the Mo and W species. The unsuccessful observation of the 60° rotamer for the Mo and W complexes is the result of its complete conversion to the 0° rotamer in both He and He/Ar carriers. For group III metal aniline complexes, the ZEKE spectrum of each complex exhibits a strong origin band, a short M+-aniline stretching progression, and several low-frequency ligand based vibrational modes. The intensities of most of the transitions can be explained by the Franck-Condon (FC) principle within the harmonic approximation. However, the intensity of the low frequency out-of-plane ring deformation mode is greatly overestimated by the FC calculations and may be caused by the anharmonic nature of the mode. Although aniline offers two possible binding modes for the metal atoms, a п binding mode is identified with the metal atom over the phenyl ring. For Ce, Pr, and Nd(cyclooctatetraene) complexes multiple band systems are observed. This is assigned to the ionization of several low-lying electronic states of the neutral complex. This observation is different from the Gd(cyclooctatetraene) complex, for which a single band system is observed. The presence of the multiple low-energy electronic states is caused by the splitting of the partially filled lanthanide 4f orbitals in the ligand field. The ZEKE spectrum of the Gd(benzene) complex exhibits a strong origin band, whereas the spectrum of Lu(benzene) displays a weak one. The benzene ring is planar in the Gd complex, but bent in the Lu complex. Dehydrogenation and C-C coupling products are observed in the reaction of La atom and ethene/propene. For the La and ethene reaction, La(C2H2) and La(C4H6) complexes are identified. With propene, C-H bond activation leads to the formation of the La(C3H4) and H-La(C3H5) complexes, whereas the C-C coupling yields the La(trimethylenemethane) complex. In addition, the La(CHCCH3) and La(CHCHCH2) isomers of La(C3H4) are observed, which are produced by the 1,2- and 1,3-hydrogen elimination of propene.