Zierkiewicz Wiktor, Kizior Beata, Michalczyk Mariusz, Jezierska Aneta, Scheiner Steve
Wrocław University of Science and Technology, Faculty of Chemistry, Wybrzeże Wyspiańskiego 27, 50-370 Wroclaw, Poland.
University of Wroclaw, Faculty of Chemistry, ul. F. Joliot-Curie 14, 50-383 Wroclaw, Poland.
Phys Chem Chem Phys. 2023 Oct 4;25(38):26172-26184. doi: 10.1039/d3cp03171c.
Quantum calculations provide a systematic assessment of the ability of Group 10 transition metals M = Pd and Pt to act as an electron donor within the context of pnicogen, chalcogen, and halogen bonds. These M atoms are coordinated in a square planar geometry, attached to two N atoms of a modified phenanthrene unit, as well as two ligand atoms Cl, Br, or I. As the Lewis acid, a series of AF molecules were chosen, which could form a pnicogen bond (A = P, As, Sb), chalcogen bond (A = S, Se, Te) or halogen bond (A = Cl, Br, I) with M. These noncovalent bonds are fairly strong, varying between 6 and 20 kcal mol, with the occupied d orbital of M acting as the origin of charge transferred to the acid. Pt forms somewhat stronger bonds than Pd, and the bond strength rises with the size of the A atom of the acid. Within the context of smaller A atoms, the bond strength rises in the order pnicogen < chalcogen < halogen, but this distinction vanishes for the fifth-row A atoms. The nature of the ligand atoms on M has little bearing on the bond strength. Based on the Harmonic Oscillator Model of Aromaticity (HOMA) index, the ZB, YB and XB bonds were shown to have only a subtle effect on the ring electronic structures.
量子计算系统地评估了第10族过渡金属M = Pd和Pt在磷族元素、硫族元素和卤族元素键的背景下作为电子供体的能力。这些M原子以平面正方形几何结构配位，连接到一个修饰菲单元的两个N原子以及两个配体原子Cl、Br或I上。作为路易斯酸，选择了一系列AF分子，它们可以与M形成磷族元素键（A = P、As、Sb）、硫族元素键（A = S、Se、Te）或卤族元素键（A = Cl、Br、I）。这些非共价键相当强，在6至20 kcal/mol之间变化，M的占据d轨道作为转移到酸上的电荷的来源。Pt形成的键比Pd稍强，并且键强度随着酸中A原子的大小而增加。在较小的A原子的情况下，键强度按磷族元素＜硫族元素＜卤族元素的顺序增加，但对于第五周期的A原子，这种区别消失了。M上配体原子的性质对键强度影响很小。基于芳香性的谐振子模型（HOMA）指数，ZB、YB和XB键对环电子结构仅具有微妙的影响。
