2,4-Pentanediolate as an Alkoxide/Diketonate “Hybrid” Ligand and the Formation of Aluminum and Zirconium Derivatives
作者:Eric J. Bierschenk、Nicholas R. Wilk、Timothy P. Hanusa
DOI:10.1021/ic201718a
日期:2011.12.5
pentanediolates decompose on heating to form Al2O3 and ZrO2. Unlike the mononuclear Al(acac)3 and Zr(acac)4 derivatives (acac = acetylacetonate), the formation of aggregates with the 2,4-pd ligand suggests that the latter has more coordinative flexibility. The geometries of several model aluminum complexes with oxygen donor ligands were studied with density functional theory methods. The optimized structures
当2,4-戊二醇(2,4-H 2 pd)去质子化时,所得的二价阴离子(2,4-pd)充当“混合”配体的一种,即具有β-结构特征的醇盐二酮。2,4-戊二醇的Al(O-发生反应小号-Bu)3和Zr(O-我-Pr)4以形成螯合多核络合物。首先分离出含铝产物,为不溶性[Al(2,4-pd)(2,4-Hpd)] n;升华后,生成了多金属物种的烃溶性混合物。质谱证据表明Al 4(2,4-pd)6和Al 5(2,4-pd)7(2,4-Hpd)存在。锆配合物被分离为加合物[Zr(2,4-pd)2 ] 2 ·(2,4-H 2 pd)。戊二醇化物在加热时分解以形成Al 2 O 3和ZrO 2。与单核Al(acac)3和Zr(acac)4衍生物(acac =乙酰丙酮酸酯)不同,具有2,4-pd配体的聚集体的形成表明后者具有更高的配位柔性。用密度泛函理论方法研究了几种具有供氧体配体的铝模型配合物的几何形状。优化的