| 摘要: | 兩當量的仳各衍生物與[C4H3N(CH2NMe2)-2]2M(NEt2)2於甲苯中反應可以得到四仳各之
[C4H3N(CH2NMe2)-2]2M(C4H4N)2 (3, M = Zr; 4, M = Hf)。相同的情形下，將
[C4H3N(CH2NMe2)-2]2M(NEt2)2與2,6-二甲基苯酚或2,6-異丙基苯酚在庚烷中反應可經
由移除二甲基胺而得到金屬烷氧化合物[C4H3N(CH2NMe2)-2]2M(OR)2 (5, M = Zr, R =
C6H3-2,6-Me2; 6, M = Hf, R = C6H3-2,6-Me2; 7, M = Zr, R = C6H3-2,6-iPr2; 8, M = Hf, R =
C6H3-2,6-iPr2)。所有化合物均經1H and 13C NMR光譜鑑定。化合物3, 4, 6, 7, 8 亦經X-
光單晶繞射鑑定。環酯類的開環聚合反應也加以研究。
Reactions of 2 equiv pyrrole with [C4H3N(CH2NMe2)-2]2M(NEt2)2 in toluene generated
tetra-pyrrolyl metal compounds [C4H3N(CH2NMe2)-2]2M(C4H4N)2 (3, M = Zr; 4, M = Hf) in
moderate yields. Similarly, treatment of metal amides [C4H3N(CH2NMe2)-2]2M(NEt2)2 with
2,6-dimethylphenol or 2,6-diisopropylphenol in heptane resulted in the elimination of
diethylamine along with the formation of the corresponding metal alkoxides
[C4H3N(CH2NMe2)-2]2M(OR)2 (5, M = Zr, R = C6H3-2,6-Me2; 6, M = Hf, R = C6H3-2,6-Me2; 7,
M = Zr, R = C6H3-2,6-iPr2; 8, M = Hf, R = C6H3-2,6-iPr2) in moderate yields. All the new
compounds were characterized by 1H and 13C NMR spectroscopy and the structures of 3, 4, 6, 7,
and 8 have also been determined by X-ray crystallographic studies. The aryloxides and the
substituted pyrrolyl ligands in both compounds 5 and 6 show fluxionality as observed by 1H
NMR signals. A kinetic study on the ring-opening polymerization of lactide exhibits a first
order reaction of lactide monomer vs compound 8. The catalytic properties of all the metal
complexes have been studied for the ring-opening polymerization of ε-caprolactone. |
