Synergistic and diminutive effects between triel bond and regium bond: Attractive interactions between π-hole and σ-hole
Synergistic and diminutive effects between triel bond and regium bond: Attractive interactions between π-hole and σ-hole
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Triel 键和 Regium 键之间的协同效应和微小效应：α-空穴和 β-空穴之间的有吸引力的相互作用
DOI：
10.1002/aoc.4806
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发表时间：
2019-04
影响因子：
3.9
通讯作者：
李庆忠
中科院分区：
文献类型：
--
作者：
张婧如;王志欣;刘树峰;程建波;李文佐;李庆忠
对MCN···ZX 3（M = Cu，Ag，Au; Z = B，Al; X = H，F）与C2 H4···AlX 3的二元配合物进行了高量子化学计算. triel键的强度取决于triel和硬币金属原子的性质以及F取代基和电子供体。分子静电势（MEP）分析证实了MCN的M-C键端存在一个σ-空穴，以AgCN < CuCN < AuCN的递增顺序与C2 H4形成区域键。配合物C2（CN）4···AuCN从MEP的角度来看是不稳定的，但当两个分子接近时产生了很大的吸引相互作用能（−38 kcal/mol），这主要是由包括轨道相互作用在内的极化引起的。这两种相互作用在C_2H_4···MCN···ZX_3三元配合物中均得到加强，而在NCAu···C_2H_4···AlX_3和C_2（CN）_4···AuCN···ZH_3三元配合物中则减弱。研究发现，C2（CN）4中的四个CN基团可以调节从协同效应到微小效应的变化。有趣的是，这两种相互作用的结合距离有一个意想不到的变化。这两种相互作用的协同性已被解释与MEP和电荷转移。当C2 H4与AlX 3或AuCN结合时，其π电子密度大大降低，甚至MEP变为正值，但仍能参与区域键或三价键。
High quantum chemical calculations have been performed for binary complexes of MCN···ZX3(M = Cu, Ag, Au; Z = B, Al; X = H, F) and C2H4···AlX3. The strength of triel bonding depends on the nature of triel and coin metal atoms as well as the F substituents and electron donors. The molecular electrostatic potential (MEP) analysis confirms a σ‐hole at the M‐C bond end of MCN, engaging in a regium bond with C2H4in an increasing sequence of AgCN < CuCN < AuCN. The complex C2(CN)4···AuCN is unstable in view of MEPs, but a big attractive interaction energy (−38 kcal/mol) is produced when both molecules approach, which is mainly caused by polarization including orbital interactions. Both types of interactions are strengthened in ternary complex of C2H4···MCN···ZX3but are weakened in NCAu···C2H4···AlX3and C2(CN)4···AuCN···ZH3. It is found that the variation from synergistic to diminutive effects can be modulated by four CN groups in C2(CN)4. Interestingly, the binding distances of both interactions have an unexpected change. The cooperativity of both interactions has been explained with MEP and charge transfer. When C2H4binds with AlX3or AuCN, its π electron density is greatly decreased and even its MEP becomes positive, but it is still able to participate in a regium bond or a triel bond.
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影响因子：
1.7
作者：
B. Zheng;Yi Liu;Lu Huang;Zhaoxu Wang;Hexiu Liu;Yuan Liu
通讯作者：
B. Zheng;Yi Liu;Lu Huang;Zhaoxu Wang;Hexiu Liu;Yuan Liu
影响因子：
1.7
作者：
Qingjie Tang;Qingzhong Li
通讯作者：
Qingjie Tang;Qingzhong Li
DOI：
10.1063/1.3626142
发表时间：
2011-08
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Hui Li;Qingzhong Li;Ran Li;Wenzuo Li;Jian-Bo Cheng
通讯作者：
Hui Li;Qingzhong Li;Ran Li;Wenzuo Li;Jian-Bo Cheng
DOI：
10.1021/j100143a018
发表时间：
1993
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
S. Reeve;W. Burns;F. Lovas;R. Suenram;K. Leopold
通讯作者：
S. Reeve;W. Burns;F. Lovas;R. Suenram;K. Leopold
DOI：
10.1039/c8cp03883j
发表时间：
2018-09
期刊：
Physical chemistry chemical physics : PCCP
影响因子：
--
作者：
W. Zierkiewicz;M. Michalczyk;S. Scheiner
通讯作者：
W. Zierkiewicz;M. Michalczyk;S. Scheiner