The study of interactions between metal ions and methane is key to understanding the C-H activation reactions involved in the generation of liquid fuels from methane. Gas phase studies serve as a model to understand these metal-ligand interactions. The interaction of the metal with methane weakens the C-H bonds and produces a substantial reduction in the C-H stretching frequencies which can be determined by measuring the vibrational spectra. This work investigates the interaction of early transition metals and metal cluster ions with methane to learn about the geometry and bonding of the reactants, intermediates, and products using photofragment spectroscopy and density functional theory. Chapters 1 and 2 discuss the motivations and techniques. Chapter 3 discusses the vibrational spectra of complexes of Ti+ and V+ with methane. The M+(CH4)1-2 complexes have different methane orientations while the M+(CH4)3-4 (M=Ti,V) are similar. Comparison of complexes for the two metals shows that methanes orient to minimize repulsion with singly- or doubly-occupied orbitals. Chapter 4 discusses the intermediates and reaction products of sequential reactions of Zr+ with CH4. Spectra are measured for Zr+(CH4)1-4 and for four dehydrogenation products. The spectra of [ZrCH4]+ and [ZrC2H8]+ are a combination of entrance and exit channel complexes, and possibly intermediates [H-Zr-CH3]+(CH4)0-1. The dehydrogenation products are observed when Zr+ sequentially reacts with three or four methanes. The products formed come from loss of H2 from n=3-4, ZrC3H +10 and ZrC4H + 14 , and loss of H and H2+H from n=4, ZrC4H +13 and ZrC4H + 15 . All of the products have methyl groups: Zr(CH3)m+(CH4)n, except for ZrC4H + 15 , which has an agostic carbene: HZrCH + 2 (CH4)3. Chapter 5 discusses the spectroscopy of vanadium cluster ions with methane. Vibrational spectra are measured for V2+(CH4)1-4, V3+(CH4)1-3, and Vx+(CH4) (x=4-8). The larger red shifts of x=5-8 suggest they are more reactive with methane than x=2-3. Chapter 6 summarizes the findings and suggests possible extensions of the experiments. The metal-methane studies can be extended to study the interaction of ethane with Ti+, Zr+, and Nb+, which can dehydrogenate ethane at room temperature. The Vx+(CH4)n cluster studies can be extended to Nbx+ as metal clusters can be more reactive than atoms.