Laser-ablated group IV transition metal atoms have been co-deposited with hydrogen selenide at 5 K in excess of argon. The metal atoms were observed to insert into the Sesingle bondH bond of hydrogen selenide to form the novel molecules HMSeH, H₂MSe, H₂M(SeH)₂ and HMSe (M = Ti, Zr, Hf). These species were identified by argon matrix-isolation IR spectroscopy, and their assignment is supported by ¹H/²D substitution as well as quantum-chemical calculations. In Particular, the molecules H₂MSe and HMSe are of interest as they are rare examples of multiple bonding between a heavier main group element and a group IV transition metal.