Yang Ming-Chung, Su Ming-Der
Department of Applied Chemistry, National Chiayi University, Chiayi 60004, Taiwan.
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung 80708, Taiwan.
ACS Omega. 2019 Feb 12;4(2):3105-3113. doi: 10.1021/acsomega.8b02469. eCollection 2019 Feb 28.
The {η-(X@C )}PtL complexes possessing three kinds of encapsulated ions (X = F, Ø, Li), three various ligands (L = CO, PPh, NHC), and twelve cage sizes (C, C, C, C, C, C, C, C, C, C, C, C) are theoretically examined by using the density functional theory (M06/LANL2DZ). The present computational results demonstrate that the backward-bonding orbital interactions, rather than the forward-bonding orbital interactions, play a dominant role in the stability of {η-(X@C )}PtL complexes. Additionally, our theoretical study shows that the presence of the encapsulated Li ion can greatly improve the stability of {η-(X@C )}PtL complexes, whereas the existence of the encapsulated F ion can heavily reduce the stability of {η-(X@C )}PtL complexes. Moreover, the theoretical evidence strongly suggests that the backward-bonding orbital interactions as well as the stability increase in the order {η-(X@C )}Pt(CO) < {η-(X@C )}Pt(PPh) < {η-(X@C )}Pt(NHC). As a result, these theoretical observations can provide experimental chemists a promising synthetic direction.
利用密度泛函理论（M06/LANL2DZ）对具有三种包封离子（X = F、Ø、Li）、三种不同配体（L = CO、PPh、NHC）以及十二种笼尺寸（C、C、C、C、C、C、C、C、C、C、C、C）的{η-(X@C )}PtL配合物进行了理论研究。目前的计算结果表明，反馈键轨道相互作用而非给体键轨道相互作用在{η-(X@C )}PtL配合物的稳定性中起主导作用。此外，我们的理论研究表明，包封Li离子的存在可显著提高{η-(X@C )}PtL配合物的稳定性，而包封F离子的存在则会严重降低{η-(X@C )}PtL配合物的稳定性。而且，理论证据有力地表明，反馈键轨道相互作用以及稳定性按{η-(X@C )}Pt(CO) < {η-(X@C )}Pt(PPh) < {η-(X@C )}Pt(NHC)的顺序增加。因此，这些理论观察结果可为实验化学家提供一个有前景的合成方向。
