Quantifying the Influence of Covalent Metal-Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes.
Quantifying the Influence of Covalent Metal-Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes.
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DOI：
10.1002/anie.202211145
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发表时间：
2022-11-07
影响因子：
16.6
通讯作者：
Daly, Scott R.
中科院分区：
文献类型：
--
作者：
Fetrow, Taylor, V;Zgrabik, Joshua;Bhowmick, Rina;Eckstrom, Francesca D.;Crull, George;Vlaisavljevich, Bess;Daly, Scott R.
长期以来，人们一直将三价镧系元素和榄系元素络合物反应活性的质的差异归因于共价金属-配体成键的差异，但很少有例子能量化这种关系的热力学方面，特别是在没有竞争变量的情况下与U3+的关系。在这里，我们报告了一系列二聚二硼酸膦与三价f金属的配合物，这些配合物表明，与具有类似尺寸的稀土元素的同构配合物相比，表明共价性增加的U−B距离如何比预期的更短，从而导致溶液解聚反应活性的显着差异。这些结果与DFT和QTAIM计算结果很好地吻合，为金属-配体共价性变化对三价铀和稀土配合物反应活性的测量效应提供了罕见的实验证据。在这里，我们报道了实验和计算研究，量化了金属-配体共价性变化对磷酸二硼酸络合物与三价铀和类似尺寸的稀土元素的反应活性的测量影响。
Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal‐ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U3+ and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalent f‐metals that show how shorter‐than‐expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal‐ligand covalency on the reactivity of trivalent uranium and lanthanide complexes. Here we report experimental and computational studies that quantify the measured effect of variations in metal‐ligand covalency on the reactivity of phosphinodiboranate complexes with trivalent uranium and similarly sized lanthanides.
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