Counteranion-Stabilized Titanium(IV) Isopolyoxocationic Clusters Isolated from Water.
Counteranion-Stabilized Titanium(IV) Isopolyoxocationic Clusters Isolated from Water.
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DOI：
10.1021/acs.inorgchem.5b01901
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发表时间：
2016-04
影响因子：
4.6
通讯作者：
Guanyun Zhang;Jie Hou;Mingzhong Li;C. Tung;Yifeng Wang
中科院分区：
文献类型：
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作者：
Guanyun Zhang;Jie Hou;Mingzhong Li;C. Tung;Yifeng Wang
通过对TiX 4的水解和缩合反应，高产率地合成了一种新的钛（IV）氧代簇合物[Ti6（Oμ）8（OtH 2）20]（8+）（Ti6（X = Cl，Br）在TBAX存在下（TBA =四丁基铵; X = Cl，Br），而TiI 4和TBAI的反应产生[Ti 8 O 12（OH 2）24]（8+）（Ti 8）。通过单晶X射线晶体学、粉末X射线衍射、电感耦合等离子体原子发射光谱法和能量色散光谱法确定了簇的结构和组成。Ti6由六配位钛（IV）原子与μ2-O原子桥接组成，结构上类似于典型的Lindqvist聚氧乙烯酸盐。基于Ti6和Ti 8的结构比较，密度泛函理论计算和光谱分析，很明显，这两个集群是稳定的卤化物抗衡阴离子通过形成氢键。这项研究不仅提出了第二个例子的钛（IV）isopolyoxocationic集群从水中分离，但也表明，抗衡阴离子通常是重要的合成分子片段的氧化钛。
A novel titanium(IV) oxo cluster comprised solely of Ti, O, and H atoms, [Ti6(Oμ)8(OtH2)20](8+) (Ti6) was synthesized in high yield via controlled hydrolysis and condensation of TiX4 (X = Cl, Br) in the presence of TBAX (TBA = tetrabutylammonium; X = Cl, Br) from water, while reactions of TiI4 and TBAI yielded [Ti8O12(OH2)24](8+) (Ti8). The structures and compositions of the clusters were determined by single-crystal X-ray crystallography, powder X-ray diffraction, inductively coupled plasma atomic emission spectrometry, and energy-dispersive spectrometry. Ti6 is comprised of six-coordinated titanium(IV) atoms bridged with μ2-O atoms, structurally similar to a typical Lindqvist polyoxometalate. On the basis of a structural comparison of Ti6 and Ti8, density functional theory calculations, and spectroscopic analysis, it is evident that both clusters are stabilized by halide counteranions via the formation of hydrogen bonds. This study not only presents the second example of a titanium(IV) isopolyoxocationic cluster isolated from water but also suggests that counteranions are generally important for synthesizing molecular fragments of titanium oxides.