Uranium atoms activate methane upon ultraviolet excitation to form the methyl uranium hydride CH3-UH, which undergoes alpha-H transfer to produce uranium methylidene dihydride, CH2UH2. This rearrangement most likely occurs on an excited-quintet potential-energy surface and is followed by relaxation in the argon matrix. These simple U + CH4 reaction products are identified through isotopic substitution ((CH4)-C-13, CD4, CH2D2) and density functional theory frequency and structure calculations for the strong U-H stretching modes. Relativistic multiconfiguration (CASSCF/CASPT2) calculations substantiate the agostic distorted C-1 ground-state structure for the triplet CH2UH2 molecule. We find that uranium atoms are less reactive in methane activation than thorium atoms. Our calculations show that the CH2UH2 complex is distorted more than CH2ThH2. A favorable interaction between the low energy open-shell U(5f) sigma orbital and the agostic hydrogen contributes to the distortion in the uranium methylidene complexes.