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

doi:10.1002/open.201700028

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

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Research output: Contribution to Journal › Article › Academic › peer-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 language	English
Pages (from-to)	410-416
Number of pages	7
Journal	ChemistryOpen
Volume	6
Issue number	3
DOIs	https://doi.org/10.1002/open.201700028
Publication status	Published - 1 Jun 2017

Funding

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.

Funders	Funder number
NWO-EW
Fundação de Amparo à Pesquisa do Estado de São Paulo	2011/20351-7, 2014/50265-3, 2008/02677-0, 2015/15176-2
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior	1938-14
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerio de Economía y Competitividad	CTQ2016-77558-R
Conselho Nacional de Desenvolvimento Científico e Tecnológico	304393/2013-4, 481560/2010-6

Keywords

molecular orbital analysis
negative trans influence
nitric oxide
ruthenium complexes
synergy

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/open.201700028

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

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.",

keywords = "molecular orbital analysis, negative trans influence, nitric oxide, ruthenium complexes, synergy",

author = "Orenha, {Renato P.} and Rocha, {Marcus V.J.} and Jordi Poater and Galembeck, {S{\'e}rgio E.} and Bickelhaupt, {F. Matthias}",

year = "2017",

month = jun,

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doi = "10.1002/open.201700028",

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T2 - Kohn–Sham Molecular Orbital and Energy Decomposition Analysis

AU - Orenha, Renato P.

AU - Rocha, Marcus V.J.

AU - Poater, Jordi

AU - Galembeck, Sérgio E.

AU - Bickelhaupt, F. Matthias

PY - 2017/6/1

Y1 - 2017/6/1

N2 - 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.

AB - 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.

KW - molecular orbital analysis

KW - negative trans influence

KW - nitric oxide

KW - ruthenium complexes

KW - synergy

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

Abstract

Funding

Keywords

UN SDGs

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