Nature of the Ru−NO Coordination Bond: Kohn–Sham Molecular Orbital and Energy Decomposition Analysis

Renato P. Orenha, Marcus V.J. Rocha, Jordi Poater, Sérgio E. Galembeck*, F. Matthias Bickelhaupt

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

We have analyzed structure, stability, and Ru−NO bonding of the trans-[RuCl(NO)(NH3)4]2+ 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(NH3)4]++NO+, [RuCl(NH3)4]2++NO, and [RuCl(NH3)4]3++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 trans 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.

Original languageEnglish
Pages (from-to)410-416
Number of pages7
JournalChemistryOpen
Volume6
Issue number3
DOIs
Publication statusPublished - 1 Jun 2017

Keywords

  • molecular orbital analysis
  • negative trans influence
  • nitric oxide
  • ruthenium complexes
  • synergy

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