Laser-ablated Ti, Zr, and Hf atoms have been codeposited at 4 K with hydrogen sulfide in excess argon. The metal atoms insert into the S-H bond of hydrogen sulfide to form the HMSH, H2MS, and H2M(SH)(2) molecules (M = Ti, Zr, Hf), which were identified on the basis of the D2S and (H2S)-S-34 isotopic substitutions. The observed vibrational frequencies of these species were reproduced by B3LYP functional calculations. The reaction mechanisms have been proposed on the potential energy surface of the studied system to account for the formation of these molecules. We have made a theoretical prediction about the H2MS complexes dehydrogenation, which can provide a novel proposal for generating hydrogen from H2S.