Completing the Heterocubane Family [Cp*AlE]4 (E = O, S, Se, and Te) by Selective Oxygenation and Sulfuration of [Cp*Al]4: Density Functional Theory Calculations of [Cp*AlE]4 and Reactivity of [Cp*AlO]4 toward Hydrolysis.
Completing the Heterocubane Family [Cp*AlE]4 (E = O, S, Se, and Te) by Selective Oxygenation and Sulfuration of [Cp*Al]4: Density Functional Theory Calculations of [Cp*AlE]4 and Reactivity of [Cp*AlO]4 toward Hydrolysis.
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DOI：
10.1021/acs.inorgchem.6b00462
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发表时间：
2016-04
影响因子：
4.6
通讯作者：
A. Stelzer;Peter Hrobárik;T. Braun;M. Kaupp;B. Braun‐Cula
中科院分区：
文献类型：
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作者：
A. Stelzer;Peter Hrobárik;T. Braun;M. Kaupp;B. Braun‐Cula
低价铝化合物[Cp*Al]4（1）与分子氧、N2O或硫反应生成杂立方烷配合物[Cp*AlX]4 [X = O（2）和S（3）]。[Cp*AlO]4（2）与（tBuO）3SiOH反应，得到[（tBuO）3SiOAlO]4（6）和Cp*H。Al团簇的结构和光谱数据得到了密度泛函理论（DFT）计算的支持，这也证明了非共价相互作用（NCI）在低聚Al（I）络合物以及[Cp*AlS]4和Se和Te的重同系物中的重要性。计算的（27）Al NMR位移表明随着硫族元素原子的电负性增加，Al中心处的去屏蔽以及较重的杂立方烷[Al 4E4]核内的显著自旋轨道屏蔽效应。在水的存在下，用额外量的硅烷醇进一步水解6导致形成[Al 4（OH）6（OH 2）2（OSiOtBu3）6]（7），其显示在勃姆石和一水硬铝石中发现的结构基序。
The subvalent aluminum compound [Cp*Al]4 (1) reacts with dioxygen, N2O, or sulfur to yield the heterocubane complexes [Cp*AlX]4 [X = O (2) and S (3)]. Treatment of [Cp*AlO]4 (2) with (tBuO)3SiOH gave [(tBuO)3SiOAlO]4 (6) and Cp*H. The structures and spectroscopic data of the Al clusters are supported by density functional theory (DFT) calculations, which also demonstrate the importance of noncovalent interactions (NCI) in oligomeric Al(I) complexes as well as in [Cp*AlS]4 and the heavier homologues of Se and Te. The computed (27)Al NMR shifts indicate a deshielding at the Al centers with increasing electronegativity of the chalcogen atom as well as significant spin-orbit shielding effects within the heavier heterocubane [Al4E4] cores. Further hydrolysis of 6 with an additional amount of silanol in the presence of water resulted in the formation of [Al4(OH)6(OH2)2(OSiOtBu3)6] (7), which shows a structural motif found in boehmite and diaspore.