New Routes to η1- and (η3?η 5)-Indenylpalladium Complexes: Synthesis, Characterization, and Reactivities

Article abstract of DOI:10.1021/om034253n

The dimer {(η⁸-Ind)Pd(μ-Cl)}₂ (6) reacts with t-BuNC to give the dimeric species {(η ¹-Ind)-(t-BuNC)Pd(μ-Cl)}2 (10), whereas reaction with PR ₃ gives the complexes (η-Ind)Pd(PR₃)Cl (R = Ph (4), Cy (7), Me (8), OMe (9)). Complexes 4 and (1-Me-Ind)Pd(PPh₃)Cl (5) can also be prepared by reacting (PhCN)₂PdCl₂ with Lilnd and PPh₃. The structural characterization of complexes 4-7, 9, and 10 by ¹H and ¹³C NMR spectroscopy and single-crystal X-ray diffraction studies has allowed an analysis of the indenyl ligand's mode of coordination, both in the solid-state and in solution. Compounds 4, 6, and 7 react with PhSiH₃ in the absence of cocatalysts, whereas reaction with ethylene requires the presence of excess MAO to give polyethylene.