Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Prediction of Catalyst with High Activity and Wide Application Scope
Theoretical Study of Hydrogenation Catalysis of Phosphorus Compound and Prediction of Catalyst with High Activity and Wide Application Scope
复制标题
DOI：
10.1021/acscatal.5b02968
复制
发表时间：
2016-06
期刊：
影响因子：
12.9
通讯作者：
Guixiang Zeng;S. Maeda;T. Taketsugu;S. Sakaki
中科院分区：
文献类型：
--
作者：
Guixiang Zeng;S. Maeda;T. Taketsugu;S. Sakaki
用密度泛函理论、CCSD(T)和ONIOM(CCSD(T)：MP2)方法研究了含磷化合物10-P-323，7-di(tert-butyl)-5-aza-2，8-dioxa-l-phosphabicyclo[3.3.0]octa-2，4，6-triene 1P及其类似物在偶氮苯与氨-硼烷转移加氢反应中的催化作用。理论计算清楚地表明，这种转移加氢反应是通过磷配体的协同催化作用进行的，磷氧化状态在+I和+III之间变化。值得注意的是，磷氧化状态的变化是1P协同催化的一个特征：主族元素不容易改变其氧化状态。这一特点不同于金属-配体协同催化中金属氧化状态不变的特点。理论计算还揭示了通过在配体上引入吸电子取代基和使用共轭平面来提高1P类化合物的催化活性。
Catalysis of phosphorus compound 10-P-323,7-di(tert-butyl)-5-aza-2,8-dioxa-l-phosphabicyclo[3.3.0]octa-2,4,6-triene 1P and its analogues in transfer hydrogenation of azobenzene with ammonia-borane (NH3BH3) was investigated using DFT, CCSD(T), and ONIOM(CCSD(T):MP2) methods. Theoretical calculations clearly reveal that this transfer hydrogenation reaction occurs through the phosphorus–ligand cooperative catalysis function with a change in the phosphorus oxidation state between +I and +III. It is noteworthy that the change in phosphorus oxidation state is a characteristic feature of the cooperative catalysis by 1P: it is not easy for a main-group element to change its oxidation state. This characteristic feature differs from that of metal–ligand cooperative catalysis in which the metal oxidation state does not change. Theoretical calculations also disclose that the catalytic activity of 1P-like compound is improved by introducing electron-withdrawing substituents to the ligand and using the conjugated plana...