Year of Publication

2014

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Arts and Sciences

Department

Chemistry

First Advisor

Dr. Dong-Sheng Yang

Second Advisor

Dr. John P. Selegue

Abstract

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.

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