提出了一项基于抗癌 VCp2Cl2 化合物衍生物及其与脱氧核糖核酸 (DNA) 代表性模型相互作用的计算研究。该衍生物是通过用H2O、NH3、OH-、Cl-、O2-和C2O42-配体取代VCp2Cl2的环戊二烯得到的。考虑了钒的氧化态IV和V，因此总共包括20个衍生配合物。使用两种不同的模型研究复合物与 DNA 的相互作用，第一个模型考虑复合物与鸟嘌呤-胞嘧啶 (G-C) 对的相互作用，第二个模型涉及复合物与相邻对（即 d(GG)）的相互作用。本研究将基于密度泛函理论的方法与电子结构方法的黄金标准耦合簇计算 (DLPNO-CCSD(T)) 进行了比较。此外，由于钒 (IV) 和 (V) 络合物的存在，保持 G-C 对和 d(GG) 对键合的氢键电子密度的变化是合理的。为此，检查从电子密度拓扑获得的量，特别是氢键临界点处的电子密度值。该方法可以识别导致上述氢键发生显着变化的钒络合物，这是理解、开发和提出金属络合物与 DNA 之间作用机制的一个关键方面。版权所有 © 2024 Elsevier Inc. 保留所有权利。

A computational study based on derivatives of the anticancer VCp2Cl2 compound and their interaction with representative models of deoxyribonucleic acid (DNA) is presented. The derivatives were obtained by substituting the cyclopentadienes of VCp2Cl2 with H2O, NH3, OH-, Cl-, O2- and C2O42- ligands. The oxidation states IV and V of vanadium were considered, so a total of 20 derivative complexes are included. The complexes interactions with DNA were studied using two different models, the first model considers the interactions of the complexes with the pair Guanine-Cytosine (G-C) and the second involves the interaction of the complexes with adjacent pairs, that is, d(GG). This study compares methodologies based on density functional theory with coupled cluster like calculations (DLPNO-CCSD(T)), the gold standard of electronic structure methods. Furthermore, the change in the electron density of the hydrogen bonds that keep bonded the G-C pair and d(GG) pairs, due to the presence of vanadium (IV) and (V) complexes is rationalize. To this aim, quantities obtained from the topology of the electron densities are inspected, particularly the value of the electron density at the hydrogen bond critical points. The approach allowed to identify vanadium complexes that lead to significant changes in the hydrogen bonds indicated above, a key aspect in the understanding, development, and proposal of mechanisms of action between metal complexes and DNA.Copyright © 2024 Elsevier Inc. All rights reserved.