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


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
Issue number3
Publication statusPublished - 1 Jun 2017


We thank São Paulo Research Foundation (FAPESP) (grants 2008/02677-0, 2011/20351-7, 2014/50265-3 and 2015/15176-2), CNPq (grants 481560/2010-6 and 304393/2013-4), CAPES (process 1938-14), The Netherlands Organization for Scientific Research (NWO-CW and NWO-EW), and Spanish MINECO (project CTQ2016-77558-R) for financial support.

FundersFunder number
Fundação de Amparo à Pesquisa do Estado de São Paulo2011/20351-7, 2014/50265-3, 2008/02677-0, 2015/15176-2
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior1938-14
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y CompetitividadCTQ2016-77558-R
Conselho Nacional de Desenvolvimento Científico e Tecnológico304393/2013-4, 481560/2010-6


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


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