Matches in SemOpenAlex for { <https://semopenalex.org/work/W2322720501> ?p ?o ?g. }
- W2322720501 endingPage "4554" @default.
- W2322720501 startingPage "4544" @default.
- W2322720501 abstract "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 the precatalyst 3 with 1.6 equiv of the standard substrate 2,2-dimethylpenten-4-ylamine leads to a fast and selective formation of substrate complex [{Cp#PN}Y(NHCH2CMe2CH2CH═CH2)2] (8). Fast cyclization was observed only after addition of more than 2 equiv of amine substrate. A noninsertive mechanism involving a six-membered transition state by a concerted C–N bond formation and N–H bond cleavage at a 3:1 substrate to complex ratio is suggested on the basis of these findings." @default.
- W2322720501 created "2016-06-24" @default.
- W2322720501 creator A5001062755 @default.
- W2322720501 creator A5003193993 @default.
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- W2322720501 creator A5009427578 @default.
- W2322720501 creator A5053511536 @default.
- W2322720501 creator A5081276020 @default.
- W2322720501 date "2011-08-11" @default.
- W2322720501 modified "2023-10-09" @default.
- W2322720501 title "Cyclopentadienylphosphazene (CpPN) Complexes of Rare-Earth Metals: Synthesis, Structural Characterization, and Hydroamination Catalysis" @default.
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