Laser-ablated group 6 metal atoms react with silane to form inserted SiH3−MH hydride intermediates, which are identified from M−H and Si−H stretching modes. Following two successive α-H-transfers, the HSi≡MH3 (M = Mo, W) silylidyne molecules are produced. These silicon−metal triple-bonded species are identified as major products from the strong M−H stretching modes through deuterium substitution and comparison with frequencies and intensities from density functional calculations and from the analogous methylidynes. The silylidynes have calculated C3v structures and longer Si−H bonds than silane, but the C3v methylidyne analogues have shorter C−H bonds than methane. The Si≡Mo and Si≡W bonds are polarized differently and have slightly lower effective bond orders than their carbon analogues. In addition, calculations for the group 6 silylidene molecules reveal Cs structures with no evidence of agostic distortion, in contrast to the corresponding methylidene molecules.