Loveday Oliver, Jover Jesús, Echeverría Jorge
Secció de Química Inorgànica, Departament de Química Inorgànica i Orgànica and Institut de Química Teòrica i Computacional (IQTC-UB), Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Inorg Chem. 2022 Aug 15;61(32):12526-12533. doi: 10.1021/acs.inorgchem.2c00921. Epub 2022 Aug 1.
We present herein a combined structural and computational analysis of the anion binding capabilities of perfluorinated polymercuramacrocycles. The Cambridge Structural Database (CSD) has been explored to find the coordination preference of these cyclic systems toward specific Lewis bases, both anionic and neutral. Interaction energies with different electron-rich species have been computed and further decomposed into chemically meaningful terms by means of energy decomposition analysis. Furthermore, we have investigated, by means of the natural resonance theory and natural bond orbital analyses how the orbitals involved in the interaction are key in determining the final geometry of the adduct. Finally, a generalization of the findings in terms of the molecular orbital theory has allowed us to understand the formation of the pseudo-octahedral second coordination sphere in linear Hg(II) complexes.
我们在此展示了对全氟聚合物环大环化合物阴离子结合能力的结构与计算相结合的分析。我们探究了剑桥结构数据库（CSD），以找出这些环状体系对特定路易斯碱（包括阴离子和中性）的配位偏好。已计算了与不同富电子物种的相互作用能，并通过能量分解分析将其进一步分解为具有化学意义的项。此外，我们借助自然共振理论和自然键轨道分析，研究了相互作用中涉及的轨道如何在决定加合物的最终几何形状方面起关键作用。最后，根据分子轨道理论对研究结果进行的概括使我们能够理解线性汞（II）配合物中伪八面体第二配位层的形成。
