期刊
ORGANOMETALLICS
卷 28, 期 5, 页码 1469-1475出版社
AMER CHEMICAL SOC
DOI: 10.1021/om8010273
关键词
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资金
- Agence Nationale de la Recherche [ANR-06-BLAN-0213]
- CNRS
- Institut Universitaire de France for a Junior IUF fellowship
- Agence Nationale de la Recherche (ANR) [ANR-06-BLAN-0213] Funding Source: Agence Nationale de la Recherche (ANR)
The coordination chemistry of the new unsymmetrical Schiff base ligand {(3,5-tBu(2)-1-OC6H4)CH=N(trans-1,2-cyclo-C6H10)N=C(Me)CH2C(CF3)(2)O}(2-) ({(ONNOCF3)-O-Ar-N-Cy}(2-)) onto Al(III) and Y(III) centers has been studied. Pro-ligand {(ONNOCF3)-O-Ar-N-Cy}H-2 (1) reacts with AlMe2Cl, Al(OiPr)(3) and Y(N(SiHMe2)(2))(3)center dot(THF)(2) to give the corresponding complexes {(ONNOCF3)-O-Ar-N-Cy}AlX (X = Cl, 5; OiPr, 6) and {(ONNOCF3)-O-Ar-N-Cy}-Y(N(SiHMe2)(2))(THF) (7) in high yields, with concomitant alkane, alcohol, and amine elimination, respectively. Single-crystal X-ray diffraction studies revealed that complexes 5 and 7 are mononuclear in the solid state with, respectively, five-coordinated distorted square-pyramidal and six-coordinated distorted octahedral geometries. Complexes 5-7 were also characterized in C6D6 solution by H-1, C-13, and F-19 NMR spectroscopy, which indicated the existence of only one isomer at room temperature. Al-OiPr complex 5 is an effective, though sluggish, initiator for the ring-opening polymerization of racemic lactide, giving polymers with a highly isotactic-enriched microstructure (P-meso = 0.87), molecular weights that match well the calculated values, and narrow polydispersities (M-w/M-n = 1.04-1.18).
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