Cyclopentadienylphosphazene (CpPN) Complexes of Rare-Earth Metals: Synthesis, Structural Characterization, and Hydroamination Catalysis

Synthesis of the first series of rare-earth-metal constrained geometry complexes containing the P-(1-adamantylamino)-P-dimethyl-tetramethyl-cyclopentadienylidene-phosphorane ligand C5Me4PMe2NHAd, {Cp#PN}H, was accomplished. This monoanionic chelate ligand is isoelectronically related to the classical dianionic cyclopentadienyl-silylamine ligand C5Me4HSiMe2NHtBu, {Cp#SiN}H2. The ligand stabilizes dialkyls [{Cp#PN}M(CH2SiMe3)2] (M = Sc, 1; Lu, 2; Y, 3; Sm, 4; Nd, 5; Pr, 6; Ce, 7) over the full range of group 3 and lanthanide cation radii. Results of NMR studies of these crystalline alkyls, XRD molecular structures, and a preliminary study revealing the high catalytic activity of complexes 3–6 in the intramolecular hydroamination/cyclization are reported. The catalytic experiments reveal a trend in activity Lu < Y < Sm < Nd ≤ Pr resembling the trend in rare-earth-metal radii. Interestingly they reveal a distinctive substrate-dependent first-order kinetic profile for all metals investigated. The reaction of t...

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