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应用密度泛函理论(DFT)的PBE0方法,金属原子采用SDD基组,H、C、O和N原子采用6-31G*基组,P和Cl原子采用6-311G*基组,对单核配合物Ir(CO)Cl(Ph2Ppy)2(1),双核配合物Ir(CO)(Cl)2(Ph2Ppy)2HgCl(2)、Ir(CO)Cl(Ph2Ppy)2HgCl2(3)和Ir(CO)(Cl)2(HgCl2)(Ph2Ppy)2HgCl(4)进行结构优化,并在优化的基础上采用基组重叠误差(BSSE)校正计算相互作用能,通过自然键轨道(NBO)和前线轨道分析研究Ir-Hg相互作用和氧化还原反应的实质.通过计算发现,Ir(CO)Cl(Ph2Ppy)2与HgCl2发生氧化还原反应得到的产物2和4比非氧化还原产物3稳定.Ir-Hg相互作用强度顺序为3<4<2,且随着Ir-Hg相互作用强度增大,HOMO轨道中Ir和Hg成分逐渐趋于接近.配合物2和4都具有一对Ir-Hg成键与反键轨道,其成键轨道的组成分别为0.5985sd0.06Hg+0.8012sd2.48Ir和0.5794sd0.05Hg+0.8151sd2.48Ir,但3中Ir与Hg的相互作用较弱,只存在弱相互作用(电荷转移作用),表现为nIr→nHg的直接作用和σIr—P(1)→nHg、σIr—C(1)→nHg的间接作用.
In the PBE0 method using density functional theory (DFT), the metal atom adopts the SDD basis, the H, C, O and N atoms adopt the 6-31G * basis set, the P and Cl atoms adopt the 6-311G * basis set, The complexes Ir (CO) Cl (Ph2Ppy) 2 (1), dinuclear complexes Ir (CO) (Cl) 2 (Ph2Ppy) 2HgCl (Cl) 2 (HgCl2) (Ph2Ppy) 2HgCl (4), and based on the optimization, the interaction energy was calculated by BSSE correction. Through the analysis of NBO and frontier orbital analysis, The interaction between Ir-Hg and the redox reaction was studied.It was found by calculation that the products 2 and 4 obtained by the redox reaction between Ir (CO) Cl (Ph2Ppy) 2 and HgCl2 were more stable than those of the non-redox product 3. Ir-Hg The order of action intensity is 3 <4 <2, and as the intensity of Ir-Hg interaction increases, the contents of Ir and Hg in HOMO orbit are gradually approached. Both complexes 2 and 4 have a pair of Ir-Hg bonding and anti- The bonding orbitals have the composition of 0.5985sd0.06Hg + 0.8012sd2.48Ir and 0.5794sd0.05Hg + 0.8151sd2.48Ir, respectively. However, the interaction between Ir and Hg in 3 is weak with only weak interaction Transfer function), the performance of nIr → nHg direct effect and Ir-P (1) → nHg, σIr-C (1) → nHg indirect effect.