The reaction of laser-ablated vanadium, niobium and tantalum atoms with hydrogen sulfide has been investigated using matrix isolation FTIR and theoretical calculations. The metal atoms inserted into the H-S bond of H2S to form the HMSH molecules （M=V, Nb, Ta）, which rearranged to H2MS molecules on annealing for Nb and Ta. The HMSH molecule can also further react with another H2S to form the H2M（SH）2 molecules. These new molecules were identified on the basis of the D2S and H234S isotopic substitutions. DFT （B3LYP and BPW91） theoretical calculations are used to predict energies, geometries, and vibrational frequencies for these novel metal dihydrido complexes and molecules. Reaction mechanism for formation of group V dihydrido complex was investigated by DFT internal reaction coordinate calculations. The dissociation of HVSH gave VS＋H2 on broad band irradiation and reverse reaction happened on annealing. Based on B3LYP calculation releasing hydrogen from HVSH is endothermic only by 13.5 kcal/mol with lower energy barrier of 16.9 kcal/mol.
