Year of Publication
Arts and Sciences
Transition metal-aromatic hydrocarbon complexes were generated in a supersonic jet and studied by zero electron kinetic energy (ZEKE) photoelectron spectroscopy and theoretical calculations. The target metal complexes were identified using time-of-flight mass spectrometry, and their ionization thresholds were located via photoionization efficiency spectroscopy. ZEKE spectroscopy was used to measure the ionization energies and vibrational frequencies of the metal complexes. Their electronic states and corresponding molecular structures were determined by comparing the experimental spectra to quantum chemical calculations and Franck-Condon simulations. In this dissertation, the metal complexes of four different aromatic hydrocarbon ligands were studied: benzene (bz), naphthalene (np), biphenyl (bp) and 1-phenyl naphthalene (phnp). In these complexes, the metal atom or ion was determined to bind to either one or two -rings. Three different bonding schemes were observed in these complexes. A twofold bonding scheme was observed in M+/M-np (M = Sc, Y, Ti, Zr, Hf), while a sixfold bonding scheme was observed in Sc+/Sc-bz and M+/M-bz2 (M = Sc, Ti, V, Cr, Mo, W). In the metal-polyphenyl complexes (i.e. Sc-, La-, and Ti-bp and Sc-phnp), twelve-fold metal-ligand bonding occurred, sixfold to two -rings of the ligand. This twelve-fold bonding mechanism requires rotation of the -rings by ~ 42 o and bending of the -rings by 40 to 57 o to clamp the metal atom or ion between the two -surfaces. Although the ground state spin multiplicities of the bare metal atoms and ions varied quite extensively, the multiplicities of the metal complexes were determined to be either singlet or doublet, except for Sc+/Sc-bz, V+-bz2, Ti-np, and Zr-np, where the triplet or quartet spin multiplicities were favored. The low spin and relatively narrower range of electron-spin multiplicities in the complexes were the result of d orbital splitting, where the degeneracy of the d orbitals was broken. Thus, the valence electrons were paired in each metal d-based molecular orbital of the complex to form low-spin singlet or doublet spin states. Some complexes favored triplet and quartet multiplicities, because the energy difference between the two highest occupied molecular orbitals was smaller than the electron pairing energy.
Sohnlein, Bradford Raymond, "PFI-ZEKE SPECTROSCOPY AND THEORETICAL CALCULATIONS OF TRANSITION METAL-AROMATIC HYDROCARBON COMPLEXES" (2007). University of Kentucky Doctoral Dissertations. 527.