Vibrational spectra of the entrance channel complexes Zr+(CH4)n(Ar) (n = 1-2) and Zr+(CH4)n (n = 3-4) and the reaction products ZrC3H10+, ZrC4H13+, ZrC4H14+, and ZrC4H15+ in the C-H stretching region (2550-3100 cm-1) are obtained using photofragment spectroscopy. The experimental spectra and simulations based on calculations at the B3LYP/aug-cc-pVTZ level of theory work together to identify the structures of the ions. The n = 1-3 entrance channel complexes show peaks around 2800 and 3000 cm-1 which indicates methane η3 hydrogen coordination, while the n = 4 complex has two peaks around 2800 cm-1 indicative of methane η2 hydrogen coordination. Observation of the low-frequency C-H stretch of an agostic carbene group, as well as the high-frequency H-H stretch, also confirms production of (H2)ZrCH2+(CH4)n-1 (n = 1-2) exit channel complexes. The observed C-H activation products formally correspond to loss of H2 from Zr+(CH4)3 and loss of H, H2, and H2 + H from Zr+(CH4)4. Comparison of experiment and simulations indicates that the activation products are Zr(CH3)2+(CH4), Zr(CH3)3+(CH4), Zr(CH3)2+(CH4)2, and HZrCH2+(CH4)3 and/or ZrCH3+(CH4)3.