AbstractDepending on the nature of the metal and the ring size, lactams react with titanocene and zircocene complexes of bis‐(trimethylsilyl)acetylene Cp2Ti(Me3SiC2SiMe3) and Cp2Zr‐(L)(Me3SiC2SiMe3) (L = Py, THF) to yield different products. In the reaction of Cp2Zr(Py)(Me3SiC2SiMe3) with N‐methyl‐€‐caprolactam a simple ligand exchange reaction occurs and the complex Cp2Zr(Me3SiC2SiMe3)[OH2)5] (1) was isolated. With β‐propiolactam the alkenyl‐amido complex Cp2)(SiMe3)][–NH2] (2) was obtained, which indicates that an agostic metal‐hydrogen interaction has taken place. The reaction of Cp2Ti(Me3‐SiC2SiMe3) with €‐caprolactam gives after elimination of the alkyne and molecular hydrogen the first early transition metal complex with a deprotonated coordinated €‐caprolactam in a η2‐amidate bonding fashion (3). The obtained complexes were characterized by NMR spectra (1, 2) and crystal structure analysis (1–3) and discussed as elemental steps in anionic ring‐opening polymerization of lactams catalyzed by metallocene‐alkyne complexes.