Photoianization and Photoelectron Spectroscopy of Organometallic Complexes

This proposal outlines the activity on the spectroscopic and imaging characterization of organometallic radicals formed in metal-mediated hydrocarbon activation reactions in the gas phase. Organometallic radicals containing heavy elements are poorly understood, yet are of great importance in organic and organometallic synthesis and homogeneous catalysis. Emphasis is placed on the reactions between lanthanide metals and small alkanes. The main results are the accurate ionization energies, metal-ligand and ligand-based vibrational frequencies, electronic states, chemical bonding, molecular structures and formation of these species. Our approach is the systematic examination of the identify and electron configuration effects of the metal elements and reactivity-structural relationships of the linear, branched, and cyclic hydrocarbons. The experimental methods include the laser-vaporization molecular beam, time-of-flight mass spectrometry, mass-analyzed threshold ionization, zero-electron-kinetic-energy, infrared-ultraviolet photoionization spectroscopy, and photoelectron velocity-map imaging. The experimental measurements are supplemented with quantum chemical calculations and spectral simulations.