This study utilizes Density Functional Theory (DFT) alongside the Chemical Bond Overlap (OP) Model and Quantum Theory of Atoms in Molecules (QTAIM) to reinterpret the well‐established trans effect in square‐planar Pt(II) complexes. Investigating ligand exchange mechanisms in trans‐[()T] (T = , , , , CO, ) via transition state localization and intrinsic reaction coordinate calculations, overlap descriptors (OP/TOP) such as density, repulsion, and polarizability are computed for Pt−T and Pt−L bonds for reactants and transition states. Through OP/TOP and QTAIM, key descriptors correlating are identified with the trans‐directing effectiveness of ligands, revealing higher electron density donation and more electron‐rich bonds in stronger trans‐directing ligands. This combined methodology offers insights into ligand trans‐directing character, enhancing understanding of their reactivity and bonding behavior.

中文翻译：

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通过分子中原子的量子理论和化学键重叠模型的视角探索 Pt(II) 配合物中的反式效应概念

本研究利用密度泛函理论 (DFT) 以及化学键重叠 (OP) 模型和分子中原子量子理论 (QTAIM) 来重新解释方形平面 Pt(II) 配合物中已确立的反式效应。研究配体交换机制反式‐[()T] (T = , , , , CO, ) 通过过渡态定位和本征反应坐标计算，计算 Pt−T 和 Pt− 的重叠描述符 (OP/TOP)，例如密度、排斥力和极化率L键用于反应物和过渡态。通过 OP/TOP 和 QTAIM，确定了与配体的反式导向有效性相关的关键描述符，揭示了更强的反式导向配体中更高的电子密度捐赠和更多的富电子键。这种组合方法提供了对配体反式导向特性的见解，增强了对其反应性和键合行为的理解。