Syntheses and reactions of fulvene-derived substituted aminoalkyl-Cp and phosphinoalkyl-Cp-Group 4 metal complexes

6-Dialkylaminofulvenes add a variety of RLi reagents to form (dialkylaminoalkyl)cyclopentadienides [C5H4CR1RNR′2]Li, which exhibit oligomeric chain structures in the solid state. Transmetallation yields the corresponding titanocene or zirconocene derivatives that often show interesting intramolecular CH activation reactions. Phosphide anion addition to 6-alkyl-fulvenes yields the analogous phosphinoalkyl-Cp reagents and subsequently their Group 4 metallocene complexes. Deprotonation of 6-dialkylamino-6-alkylfulvenes generates enamino-substituted Cp-ligands. Their metal complexes undergo intramolecular Mannich reactions to yield C3-bridged ansa-metallocene products. Treatment of 6-dimethylaminofulvene with LiNHAr reagents leads to amine exchange and opens a synthetic route to “CpCN”MX2 “constrained geometry” catalysts. LiNHR addition to some 6-alkylfulvenes represents an alternative entry to this important class of compounds. The corresponding “CpCP”MX2 systems are derived from the analogous LiPHR addition reaction. Many typical reactions of the new fulvene-derived metal complexes are presented and discussed.