In this paper, we have explored the bonding properties of a series of mononuclear half-sandwich nd⁷ anticancer complexes based on N∩O dendritic scaffolds (L) using two functionals (B3LYP and BP86) with generic basis set (LanL2DZ for transition metals (as well as halogen atoms) and 6-311 + G (d,p) for others atoms. The geometry optimization of structures have led to the adoption of the piano-stool environment and the formation of kings of intermolecular hydrogen bonding: CH … X (Cl,Br) (2.619–2.954) and CH...O (2.266–2.973 Å) interaction. The metal (M)-bromine bond distances have shown to be significantly higher than metal-chlorine ones. In chloride complexes, salicylaldimine ligand-Co²⁺ (−3097.15 kJ/mol) and salicylaldimine ligand-Ir²⁺ (−3436.78 kJ/mol) interactions are stronger. Except for cobalt complexes, the interaction energies are underestimated by B3LYP functional, by contrast B3LYP HOMO-LUMO gaps obtained are highly greater. The metal ion affinity (MIA) is increasing in the order: ${\text{Ir}}^{+2}<{\text{Rh}}^{+2}<{\text{Co}}^{+2}$ for both halogen ligands adopted, exception for picolinate and salicylaldimine ligands. Our results also show that the metal … oxygen, metal … nitrogen and metal … halogen interactions are closed-shell interaction. From the contribution of the $\Delta \mathbf{E}{}_{\mathit{orb}}$ term in the ranges 4.06–98.61% (X = Cl) and 10.29–99.87% (X = Br), the nature of the ${\left[\mathbf{M}\mathbf{L}\mathbf{C}{\mathbf{P}}^{\ast }\right]}^{\mathit{n}}(\mathit{n}=0\left(\mathit{A};\mathit{B};\mathit{C}\right),\mathit{n}=-2(\mathit{D};\mathit{E}))$ … ${\mathit{X}}^{-}$ interaction turned out to be mainly dependent on the transition metal and halogen atom involved. The smallest back-donation observed for chloride complexes corresponding to the highest barrier to the formation of $\left[\mathbf{M}\mathbf{L}\mathbf{C}{\mathbf{P}}^{\ast }\right]-\mathit{X}$ bond traduces that the fact that chloride complexes are the least reactive. In the majority of cases, larger donation is obtained compared to back-donation showing that the possibility of ${\left({\left[\mathbf{L}\mathbf{C}{\mathbf{P}}^{\ast }\right]}^{-n}\right)}^{{\delta }^{-}}\leftarrow$ ${\left({\left[\mathbf{M}\mathbf{X}\right]}^{+}\right)}^{\delta +}$ charge separation can be expected. For α rings of chloride complexes, B3LYP HOMA indexes are higher than those estimated by PB86 functional. Conversely, opposite results were found for their bromide counterparts.

在本文中，我们已经探索了一系列单核半夹心ND的粘结性能^7个基于抗癌络合物N∩O使用两个函（B3LYP和BP86）与通用基组树突状支架（L）（对于LANL2DZ过渡金属（以及卤素原子）和其他原子的6-311 + G（d，p）。结构的几何优化使钢琴凳环境得以采用，并形成了分子间氢键之王：CH…X （Cl，Br）（2.619-2.954）和CH ... O（2.266-2.973Å）相互作用。金属（M）-溴键的距离已显着高于金属-氯键的距离。在氯化物络合物中，水杨醛亚胺配体-Co 2 ⁺（-3097.15 kJ / mol）和水杨醛亚胺配体-Ir ²⁺（−3436.78 kJ / mol）相互作用更强。除钴配合物外，B3LYP官能团低估了相互作用能，相反，获得的B3LYP HOMO-LUMO间隙要大得多。金属离子亲和力（MIA）按以下顺序增加：${\text{铱}}^{+2}<{\text{铑}}^{+2}<{\text{有限公司}}^{+2}$对于采用的两个卤素配体，吡啶甲酸和水杨醛亚胺配体除外。我们的结果还表明，金属……氧，金属……氮和金属……卤素相互作用是闭壳相互作用。从的贡献$\Delta \mathbf{Ë}{}_{\mathit{宝珠}}$ 该术语的性质在4.06–98.61％（X = Cl）和10.29–99.87％（X = Br）之间 ${\left[\mathbf{中号}\mathbf{大号}\mathbf{C}{\mathbf{P}}^{\ast }\right]}^{\mathit{ñ}}（\mathit{ñ}=0（\mathit{一种};\mathit{乙};\mathit{C}），\mathit{ñ}=-2（\mathit{d};\mathit{Ë}））$ … ${\mathit{X}}^{-}$相互作用主要取决于所涉及的过渡金属和卤素原子。观察到的最小的氯化物络合物的背捐赠对应于最高的形成障碍$\left[\mathbf{中号}\mathbf{大号}\mathbf{C}{\mathbf{P}}^{\ast }\right]-\mathit{X}$键表明氯化物络合物的反应性最低。在大多数情况下，相比于反向捐赠，可以获得更大的捐赠，这表明了${（{\left[\mathbf{大号}\mathbf{C}{\mathbf{P}}^{\ast }\right]}^{-ñ}）}^{{\delta }^{-}}\leftarrow$ ${（{\left[\mathbf{中号}\mathbf{X}\right]}^{+}）}^{\delta +}$可以预期电荷分离。对于氯化物配合物的α环，B3LYP HOMA指数高于PB86功能估计的那些。相反，他们的溴化物对应物却发现了相反的结果。