Treatment of 6‐R‐2‐(Me3SiCH2)C5H3N (R = H or Me) with nBuLi in diethyl ether affords the dimeric lithium complexes [{2‐(6‐R‐Pyr)(Me3Si)}CHLi·OEt2]2 (Pyr = pyridine, C5H3N) in high yields. In these complexes, the two anionic ligands have different bonding modes. These complexes easily undergo insertion reactions with nitriles to form six‐membered cyclic dimeric complexes in good yields. Further transmetalations of the six‐membered cyclic complexes with CuCl, SnCl4, or CoCl2 allow the formation of new metal complexes that maintain the frameworks of the six‐membered metallacycles. All complexes represented above were fully characterized by methods including single‐crystal X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)