Reactions of laser-ablated, excited group 11 metal atoms with CH3F isotopomers have been carried out, leading to the generation of CH3-MY and CH2F-M complexes for Cu, Ag, and Au in addition to smaller complexes for gold. The products in the infrared spectra identified on the basis of their frequencies, isotopic shifts, and correlation with DFT calculated frequencies reveal that M-F insertion by the coinage metals and H atom release readily occur. The relatively low dissociation energies of CH3-AuF to give several smaller Au complexes are consistent with the observation of these fragments. The C-Au bonds of CF-AuH and CH2-AuF exhibit considerable pi character, and the methylidene CH2-AuF contains a true double bond. In contrast, the bond orders of CH2-Au and CH2-AuH are lower, indicating that F bonded to Au contracts the gold 5d orbitals for better overlap with the carbon 2p orbital for pi bonding.