The primary products in reactions of laser-ablated group 5 metal atoms with ethane were identified in argon matrix IR spectra and characterized via density functional theory computations. The second- and third-row transition metals Nb and Ta produced insertion, metallacyclopropane, vinyl trihydrido, and anionic ethylidyne complexes (CHCH-MH, (CH)-MH, CH═CH-MH, and CHC≡MH), while the first-row transition metal V yielded only the insertion and metallacyclopropane products. The energetically higher ethylidenes and neutral ethylidynes (CHCH═MH and CHC[Formula: see text]MH) were not detected. The unique anionic ethylidynes are the most stable anionic species in the Nb and Ta systems. Evidently back-donation from the metal center to the C-C π* orbital is stronger than that in the group 6 metal analogue but weaker than that in the corresponding group 4 metal complex. The C-M bond for the Nb and Ta ethylidyne anions is a true triple bond.
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