Fakultät für Chemie , Universität Wien , Zentrum für Röntgenstrukturanalyse , 1090 Wien , Austria.
Department of Chemistry , Umeå University , 901 87 Umeå , Sweden.
Inorg Chem. 2019 Jan 7;58(1):106-113. doi: 10.1021/acs.inorgchem.8b01740. Epub 2018 Dec 13.
Since the first successful triol-functionalization of the Anderson polyoxometalates, the six protons of their central octahedron X(OH) (X-heteroatom, p- or d-element) have been considered as a prerequisite for their functionalization with tripodal alcohols, and therefore, the functionalization of Anderson structures from the unprotonated sides have never been reported. Here, we describe the triol-functionalization of [Cr(OH)WO] leading to the single-side grafted anions [Cr(OCH)CRWO] (CrW-tris-R, R = -CH, -NH, -CHOH) and the unprecedented double-side functionalized anion [Cr((OCH)CCH)WO] (CrW-(tris-CH)), despite the lack of protons in the parent anion in the solid state. CrW-(tris-CH) demonstrates the first example of double-side functionalized Anderson POT with the partially one-side protonated corresponding parent anion. The new heteropolytungstates were characterized by single-crystal X-ray diffraction, elemental analysis, Fourier-transform infrared spectroscopy, thermal gravimetric analysis, cyclic voltammetry, and electrospray ionization mass spectrometry. Density functional theory calculations were performed to investigate and compare the stability among the different isomers of the parent anion [Cr(OH)WO].
自 Anderson 多金属氧酸盐首次成功实现三功能化以来，其中心八面体 X(OH)（X-杂原子、p 或 d 元素）的六个质子被认为是其与三齿醇官能化的前提条件，因此，从未报道过从未质子化的一侧对 Anderson 结构进行官能化。在这里，我们描述了[Cr(OH)WO]的三醇官能化，导致单侧接枝阴离子[Cr(OCH)CRWO]（CrW-tris-R，R = -CH，-NH，-CHOH）和前所未有的双侧官能化阴离子[Cr((OCH)CCH)WO]（CrW-(tris-CH)），尽管在固态母体阴离子中缺乏质子。CrW-(tris-CH)展示了首例部分单侧质子化相应母体阴离子的双侧官能化 Anderson POT。新的杂多钨酸盐通过单晶 X 射线衍射、元素分析、傅里叶变换红外光谱、热重分析、循环伏安法和电喷雾电离质谱进行了表征。进行了密度泛函理论计算以研究和比较母体阴离子[Cr(OH)WO]的不同异构体之间的稳定性。
