Department of Chemistry and Biochemistry, University of Arizona, Tucson, Arizona 85721, USA.
Dalton Trans. 2011 Feb 7;40(5):1041-6. doi: 10.1039/c0dt01218a. Epub 2010 Dec 14.
Lanthanide hydroxide cluster complexes with acetylacetonate were synthesized by the hydrolysis of the corresponding hydrated lanthanide acetylacetonates in methanol in the presence of triethylamine. Polymeric lanthanide hydroxide complexes based on diamond-shaped dinuclear repeating units of Ln(2)(CH(3)CO(3))(2) (Ln = La, Pr) and discrete complexes featuring a tetranuclear distorted cubane core of Ln(4)(μ(3)-OH)(2)(μ(3)-OCH(3))(2) (Ln = Nd, Sm) and a nonanuclear core of Ln(9)(μ(4)-O)(μ(4)-OH)(μ(3)-OH)(8) (Ln = Eu-Dy, Er, Yb) were obtained. The dependence of the cluster nuclearity on the identity of the lanthanide ion is rationalized in terms of the influences of a metal ion's Lewis acidity and the sterics about the Ln-OH unit on the kinetics of the assembly process that leads to a particular cluster.
在三乙胺存在下，通过甲醇中相应水合镧系乙酰丙酮盐的水解合成了乙酰丙酮根桥联的镧系氢氧化物簇合物。基于Ln(2)(CH(3)CO(3))(2)（Ln = La, Pr）的钻石形双核重复单元的聚合镧系氢氧化物配合物和具有Ln(4)(μ(3)-OH)(2)(μ(3)-OCH(3))(2)（Ln = Nd, Sm）的四核扭曲立方烷核和Ln(9)(μ(4)-O)(μ(4)-OH)(μ(3)-OH)(8)（Ln = Eu-Dy, Er, Yb）的非核核的离散配合物。根据金属离子的路易斯酸度和 Ln-OH 单元的空间位阻对导致特定簇的组装过程动力学的影响，合理地解释了簇核数与镧系元素离子的关系。
