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首页> 外文期刊>Chemistry: A European journal >Scission of carbon monoxide using TaR_3, R = (N(tBu)Ph) or OSi(tBu)_3: A DFT investigation
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Scission of carbon monoxide using TaR_3, R = (N(tBu)Ph) or OSi(tBu)_3: A DFT investigation

机译：使用TaR_3，R =（N（tBu）Ph）或OSi（tBu）_3切断一氧化碳：DFT研究

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摘要

The experimentally known reduction of carbon monoxide using a 3-coordinate [Ta(silox)_3] (silox = OSi-(tBu)_3) complex initially forms a ketenylidene [(silox)_3Ta-CCO], followed by a dicarbide [(silox)_3Ta-CC-Ta-(silox)_3] structure. The mechanism for this intricate reaction has finally been revealed by using density functional theory, and importantly a likely structure for the previously unknown intermediate [(silox)_3Ta-CO]_2 has been identified. The analysis of the reaction pathway and the numerous intermediates has also uncovered an interesting pattern that results in CO cleavage, that being scission from a structure of the general form [(silox)_3Ta-C _nO] in which n is even. When n is odd, cleavage cannot occur. The mechanism has been extended to consider the effect of altering both the metal species and the ligand environment. Specifically, we predict that introducing electron-rich metals to the right of Ta in the periodic table to create mixed-metal dinuclear intermediates shows great promise, as does the ligand environment of the Cummins-style 3-coordinate amide structure. This latter environment has the added complexity of improved electron donation from amide rotation that can significantly increase the reaction exothermicity.
机译：实验上已知的使用三坐标[Ta（silox）_3]（silox = OSi-（tBu）_3）络合物还原一氧化碳的方法最初是形成亚烯基[（silox）_3Ta-CCO]，然后生成二碳化物[（silox） ）_3Ta-CC-Ta-（silox）_3]结构。最终，通过使用密度泛函理论揭示了这种复杂反应的机理，并且重要的是，已经确定了先前未知的中间体[（silox）_3Ta-CO] _2的可能结构。对反应途径和众多中间体的分析还发现了导致CO裂解的有趣模式，即从n为偶数的一般形式[（silox）_3Ta-C _nO]的结构上断裂。当n为奇数时，裂解不会发生。该机制已被扩展为考虑改变金属种类和配体环境的影响。具体而言，我们预测将富电子的金属引入到元素周期表中Ta的右边，以创建混合金属双核中间体，正如康明斯式3配位酰胺结构的配体环境一样，具有广阔的前景。后一种环境增加了酰胺旋转带来的电子给体改善的复杂性，这可以显着增加反应放热性。

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