Probing the Origin of Challenge of Realizing Metallaphosphabenzenes: Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes.
Probing the Origin of Challenge of Realizing Metallaphosphabenzenes: Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes.
复制标题
探讨实现金属磷苯的挑战的根源：金属吡啶中不利的 1,2-迁移在金属磷苯中变得可行
DOI：
10.1038/srep28543
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发表时间：
2016-06-24
影响因子：
4.6
通讯作者：
Zhu J
中科院分区：
文献类型：
--
作者：
Wu J;Hao Y;Zhu J
金属苯化合物引起了理论和实验化学家的极大兴趣。然而，金属磷杂苯从未被合成。因此，了解合成金属磷杂苯的挑战的起源对实验学家来说尤为紧迫。现在，密度泛函理论（DFT）计算已经进行了研究这个问题。我们的研究结果表明，1，2-迁移在金属吡啶是不利的，而这样的1，2-迁移在金属磷杂苯是可行的，这可以合理化的磷不愿意参与π键。此外，π-供体配体和5d过渡金属可以稳定金属磷杂苯。与氢化物和甲基迁移相比，由于M=P键的极化，氯离子迁移具有相对较低的活化能垒。CO配体的引入降低了金属中心与磷原子的相互作用，进一步降低了迁移反应的反应势垒。这些发现有助于合成化学家实现第一个金属磷杂苯。
Metallabenzenes have attracted considerable interest of both theoretical and experimental chemists. However, metallaphosphabenzene has never been synthesized. Thus, understanding the origin of the challenge of synthesizing metallaphosphabenzene is particularly urgent for experimentalists. Now density functional theory (DFT) calculations have been carried out to examine this issue. Our results reveal that the 1,2-migration in metallapyridines is unfavorable whereas such a 1,2-migration in metallaphosphabenzenes is feasible, which can be rationalized by the reluctance of phosphorus to participate in π bonding. In addition, π-donor ligands and the 5d transition metals can stabilize metallaphosphabenzenes. Compared with hydride and methyl migration, the chloride migration has a relatively lower activation barrier due to the polarization of the M=P bond. CO ligand could further decrease the reaction barrier of the migration due to the reduction of the interaction between the metal centre and the phosphorus atom. All of these findings could help synthetic chemists to realize the first metallaphosphabenzene.