当前位置：
X-MOL 学术
›
Int. J. Quantum Chem.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Cooperative effects between triel and halogen bonds in complexes of pyridine derivatives: An opposite effect of the nitrogen oxidation on triel and halogen bonds
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2020-08-19 , DOI: 10.1002/qua.26429 Ruijng Wang 1 , Bo Xiao 1 , Wenzuo Li 1 , Qingzhong Li 1
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2020-08-19 , DOI: 10.1002/qua.26429 Ruijng Wang 1 , Bo Xiao 1 , Wenzuo Li 1 , Qingzhong Li 1
Affiliation
|
Ab initio calculations are performed for binary complexes of TrR3···4‐PyX/4‐OPyX and 4‐PyX/4‐OPyX···N‐base (Tr = B, Al; R = H, Cl, Br, I; X = Cl, Br, I; N‐base = HCN, NHCH2, NH3). The halogen bond (XB) is weak but becomes stronger in the HCN(sp) < NH3(sp3) < NHCH2(sp2) pattern. Nitrogen oxidation can enhance the XB a little. The triel bond (TrB) is very strong, with interaction energy ranging from −35 to −58 kcal/mol. The TrB is weaker for the heavier halogen atom in the AlR3 complex, while no such dependence is found in the BR3 complex. The oxygen atom of 4‐OPyX engages in a weaker TrB than the nitrogen atom of 4‐PyX, inconsistent with the negative molecular electrostatic potentials (MEPs) on both atoms. Both TrB and XB are strengthened in TrR3···4‐PyX/4‐PyOX···N‐base. The binding distance of the stronger TrB is shortened to less than that of the weaker XB, which is in contrast to that in BF3···NCH···NCH, where the stronger TrB has a larger shortening in the binding distance. The cooperativity is explained by MEP and charge transfer.
中文翻译：
吡啶衍生物配合物中的三键和卤素键之间的协同作用：氮氧化对三键和卤素键的相反作用
从头算是针对TrR 3 ···4-PyX / 4-OPyX和4-PyX / 4-OPyX···N-基的二元配合物（Tr = B，Al; R = H，Cl，Br， I； X = Cl，Br，I； N-碱= HCN，NHCH 2，NH 3）。卤素键（XB）较弱，但在HCN（sp）<NH 3（sp 3）<NHCH 2（sp 2）模式中变强。氮氧化可以稍微增强XB。Triel键（TrB）非常强，相互作用能范围为-35至-58 kcal / mol。TrB对于AlR 3配合物中较重的卤素原子较弱，而在BR 3中未发现这种依赖性复杂。4-OPyX的氧原子比4-PyX的氮原子参与的TrB弱，这与两个原子上的负分子静电势（MEP）不一致。TrB和XB都在TrR 3 ···4-PyX / 4-PyOX···N基中得到增强。较强的TrB的结合距离缩短至小于较弱的XB的结合距离，这与BF 3 ···NCH···NCH的情况相反，在BF 3 ···NCH···NCH中，较强的TrB的结合距离缩短较大。MEP和电荷转移解释了协同性。
更新日期：2020-08-19
中文翻译：
吡啶衍生物配合物中的三键和卤素键之间的协同作用：氮氧化对三键和卤素键的相反作用
从头算是针对TrR 3 ···4-PyX / 4-OPyX和4-PyX / 4-OPyX···N-基的二元配合物（Tr = B，Al; R = H，Cl，Br， I； X = Cl，Br，I； N-碱= HCN，NHCH 2，NH 3）。卤素键（XB）较弱，但在HCN（sp）<NH 3（sp 3）<NHCH 2（sp 2）模式中变强。氮氧化可以稍微增强XB。Triel键（TrB）非常强，相互作用能范围为-35至-58 kcal / mol。TrB对于AlR 3配合物中较重的卤素原子较弱，而在BR 3中未发现这种依赖性复杂。4-OPyX的氧原子比4-PyX的氮原子参与的TrB弱，这与两个原子上的负分子静电势（MEP）不一致。TrB和XB都在TrR 3 ···4-PyX / 4-PyOX···N基中得到增强。较强的TrB的结合距离缩短至小于较弱的XB的结合距离，这与BF 3 ···NCH···NCH的情况相反，在BF 3 ···NCH···NCH中，较强的TrB的结合距离缩短较大。MEP和电荷转移解释了协同性。
京公网安备 11010802027423号