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- W2034996086 abstract "Aminodiolate ligands, RN(CH2CH2C(O)R‘2)2 (1a−e), allow the isolation of soluble, monomeric zirconium dialkyl complexes, [RN(CH2CH2C(O)R‘2)2]ZrR‘ ‘2 (2a−e, 5, 6). The fluxional behavior and thermal stability of these complexes are strongly dependent on the nature of the substituents at the nitrogen center, with smaller substituents (R = Me; 2a,b, 5, 6) increasing the rigidity and thermal stability of the complexes. Complexes bearing tert-butyl groups (2c,d) readily undergo thermal decomposition by elimination of isobutene. Thermal ortho metalation of the chiral complex Zr[((S)-PhC(H)Me)N(CH2CH2C(O)Me2][CH2Ph]2 (2e) affords the chiral metallacycle Zr[N{CH2CH2C(O)Me2}2{((S)-2-C6H4C(H)Me}][CH2Ph] (7), which has been structurally characterized. Reaction of 7 with 1 equiv of aryl aldehyde (ArC(O)H; Ar = Ph, β-naphthyl) results in regiospecific insertion of the aldehyde into the phenyl−zirconium bond. The resulting aminotriolate complex Zr[N{CH2CH2C(O)Me2}2{((S)-2-((R)-(β-naphthyl)CH(O))-C6H4C(H)Me}][CH2Ph] (8b) is formed in 91% de and has been characterized by X-ray crystallography. Further insertion of ArC(O)H into the remaining Zr−benzyl bond of 8b proceeds with poorer stereochemical control. Complex 7 also catalyzes the slow cyclotrimerization of phenylacetylene to 1,2,4- and 1,3,5-triphenylbenzene (2.5 turnovers/day). Complexes 2b,d and 7 function as precatalysts for ethylene polymerization when treated with MAO activator, although the activity is very low." @default.
- W2034996086 created "2016-06-24" @default.
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- W2034996086 date "2000-01-20" @default.
- W2034996086 modified "2023-10-11" @default.
- W2034996086 title "Dibenzylzirconium Complexes of Chelating Aminodiolates. Synthesis, Structural Studies, Thermal Stability, and Insertion Chemistry" @default.
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- W2034996086 doi "https://doi.org/10.1021/om9907324" @default.
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