The zirconium silyl complex CpCp ★Zr[Si(SiMe 3) 3]Me ( 1; Cp = η 5-C 5H 5; Cp ★ = η 5-C 5Me 5) reacts with nitriles RCN (R = Me, CHCH 2, Ph) to form the azomethine derivatives CpCp ★Zr[NC(R)Si(SiMe 3) 3]Me ( 2, R = Me; 3, R = CHCH 2; 4, R = Ph). Pyridine reacts with 1 to give a 75% yield of CpCp ★Zr[NC 5H 5Si(SiMe 3) 3]Me ( 5), which results from 1,2-addition of the ZrSi bond of 1 to pyridine. These reactions provide the first examples of nitrile and pyridine insertions into a transition metal-silicon bond. The related silyl complexes Cp 2Zr[Si(SiMe 3) 3]Me and CpCp ★Zr[Si(SiMe 3) 3]Cl are much less reactive toward nitriles and pyridine.