Orenha Renato P, Rocha Marcus V J, Poater Jordi, Galembeck Sérgio E, Bickelhaupt F Matthias
Departamento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, USP Ribeirão Preto-SP 14040-901 Brazil.
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling (ACMM) Vrije Universiteit Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands.
ChemistryOpen. 2017 Mar 30;6(3):410-416. doi: 10.1002/open.201700028. eCollection 2017 Jun.
We have analyzed structure, stability, and Ru-NO bonding of the -[RuCl(NO)(NH)] complex by using relativistic density functional theory. First, we focus on the bond dissociation energies associated with the three canonical dissociation modes leading to [RuCl(NH)]+NO, [RuCl(NH)]+NO, and [RuCl(NH)]+NO. The main objective is to understand the Ru-NO bonding mechanism in the conceptual framework of Kohn-Sham molecular orbital theory in combination with a quantitative energy decomposition analysis. In our analyses, we have addressed the importance of the synergism between Ru-NO σ-donation and π-backdonation as well as the so-called negative influence of the Cl ligand on the Ru-NO bond. For completeness, the Ru-NO bonding mechanism is compared with that of the corresponding Ru-CO bond.
我们运用相对论密度泛函理论分析了-[RuCl(NO)(NH)]配合物的结构、稳定性和Ru-NO键。首先，我们关注与三种典型解离模式相关的键解离能，这三种模式分别会生成[RuCl(NH)]+NO、[RuCl(NH)]+NO和[RuCl(NH)]+NO。主要目的是在Kohn-Sham分子轨道理论的概念框架内，结合定量能量分解分析，理解Ru-NO键的形成机制。在我们的分析中，我们探讨了Ru-NO σ-给予和π-反馈之间协同作用的重要性，以及Cl配体对Ru-NO键的所谓负面影响。为全面起见，将Ru-NO键的形成机制与相应的Ru-CO键的形成机制进行了比较。
