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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of the Structural and Fluxional Behavior of Copper(I)-Octahydrotriborate Complex
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Theoretical Study of the Structural and Fluxional Behavior of Copper(I)-Octahydrotriborate Complex

机译：铜（I）-八氢三硼酸铜配合物的结构和流动行为的理论研究

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摘要

The geometrical structures of [B_3H_8]~- and [ClCuB_3H_8]~- compounds have been investigated by means of ab initio calculations, using the MP2 level of theory, and density functional theory (DFT) method. The [ClCuBV_3H_8]~- (3a) complex structure, in which two boron atoms were bound to the copper atom via two B-H-Cu bridge hydrogen bonds (one bridge bond for each boron), was the most stable. Its MP2 and DFT calculated geometry is comparable to that of B_4H_10. In addition, the DFT calculated vibrational frequencies are in good agreement with experimental values. On the other hand, the most favorable interconversion of 3a structure was found to proceed with a low activation barrier (6.5 kcal mol~(-1)). This is consistent with the NMR spectra and confirms the rapid fluxional behavior for this complex. Moreover, the isomerization leading to 3a, from the less stable structure 3c, also proceeds with a low energy barrier (5.2 kcal mol~(-1)), whereas the activation barrier of reverse rearrangement is negligible. The calculated energy barriers of the rearrangement between the less stable structures 3b and 3c are also very small (1.2 kcal mol~(-1)).
机译：[B_3H_8]〜和[ClCuB_3H_8]〜-化合物的几何结构已通过从头算的方法，使用MP2理论水平和密度泛函理论（DFT）方法进行了研究。最稳定的是[ClCuBV_3H_8]〜-（3a）络合物结构，其中两个硼原子通过两个B-H-Cu桥氢键（每个硼一个桥键）结合到铜原子上。其MP2和DFT计算的几何形状与B_4H_10相当。此外，DFT计算的振动频率与实验值非常吻合。另一方面，发现3a结构的最有利的相互转化以低的活化势垒（6.5kcal mol·（-1））进行。这与NMR谱图一致，并证实了该络合物的快速通量行为。而且，由不稳定的结构3c导致的3a的异构化也以低能量势垒（5.2kcal mol·（-1））进行，而反向重排的活化势垒可忽略不计。计算出的不稳定结构3b和3c之间重排的能垒也很小（1.2 kcal mol〜（-1））。

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