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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >The role of the central atom in structure and reactivity of polyoxometalates with adjacent d-electron metal sites. Computational and experimental studies of gamma-[(X-n+ O-4)Ru-III (2)(OH)(2)(M-FM)(10)O-32]((8-n))- for M-FM = Mo and W, and X= Al-III,
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The role of the central atom in structure and reactivity of polyoxometalates with adjacent d-electron metal sites. Computational and experimental studies of gamma-[(X-n+ O-4)Ru-III (2)(OH)(2)(M-FM)(10)O-32]((8-n))- for M-FM = Mo and W, and X= Al-III,

机译：中心原子在多金属氧酸盐与相邻d电子金属位点的结构和反应性中的作用。 γ-[（X-n + O-4）Ru-III（2）（OH）（2）（M-FM）（10）O-32]（（8-n））-的计算和实验研究-FM = Mo和W，X = Al-III，

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摘要

The role of the central atom X in the structure and reactivity of di-Ru-substituted gamma-Keggin polyoxometalates (POMS), gamma-[(Xn+O4)Ru-2(III)(OH)(2)(M-FM)(10)O-32]((8-n)-), where M-FM = Mo and W, and X = Al-III, Si-IV, P-V, and S-VI, was computationally investigated. It was shown that for both M-FM = Mo and W the nature of X is crucial in determining the lower lying electronic states of the polyoxoanions, which in turn likely significantly impacts their reactivity. For the electropositive X = Al-III the ground state is a low-spin state, while for the more electronegative X = S-VI the ground state is a high-spin state. In other words, the heteroatom X can be an '' internal switch '' for defining the ground electronic states of the gamma-M-2-Keggin POMs. The obtained trends, in general, are less pronounced for MFM = Mo than for W. On the basis of the comparison of the calculated energy gaps between low-spin and high-spin states of polytungstates and polymolybdates, we predict that the gamma-M-2-Keggin polytungstates could be more reactive than their polymolybdate analogues. For purposes of experimental verification the computationally predicted and evaluated polytungstate gamma-[(SiO4)Ru-2(III)(OH)(2)(-)(OH2)(2)W10O32](4-) was prepared and characterized.
机译：中心原子X在双Ru取代的γ-Keggin多金属氧酸盐（POMS），γ-[（Xn + O4）Ru-2（III）（OH）（2）（M-FM）的结构和反应性中的作用）（10）O-32]（（8-n）-），其中M-FM = Mo和W，X = Al-III，Si-IV，PV和S-VI，已得到计算研究。结果表明，对于M-FM = Mo和W而言，X的性质对于确定聚氧阴离子的较低电子态至关重要，这反过来可能会显着影响其反应性。对于正电X = Al-III，基态为低自旋态，而对于负电X = S-VI，基态为高自旋态。换句话说，杂原子X可以是“内部开关”，用于定义γ-M-2-KegginPOM的接地电子状态。通常，对于MFM = Mo，获得的趋势不如W明显。在比较计算得到的多钨酸盐和多钼酸盐的低旋态和高旋态之间的能隙之后，我们预测γ-M -2-Keggin多钨酸盐可能比其多钼酸盐类似物更具反应性。为了进行实验验证，制备并表征了计算预测和评估的聚钨酸γ-[（SiO4）Ru-2（III）（OH）（2）（-）（OH2）（2）W10O32]（4-）。

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