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

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

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
Externally published	Yes

Keywords

molecular orbital analysis
negative trans influence
nitric oxide
ruthenium complexes
synergy

ASJC Scopus subject areas

General Chemistry

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10.1002/open.201700028

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@article{b5751588acd94466964720f41a970822,

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\}",

note = "Publisher Copyright: {\textcopyright} 2017 The Authors. Published by Wiley-VCH Verlag GmbH \& Co. KGaA.",

year = "2017",

month = jun,

day = "1",

doi = "10.1002/open.201700028",

language = "English",

volume = "6",

pages = "410--416",

journal = "ChemistryOpen",

issn = "2191-1363",

publisher = "John Wiley \& Sons Inc.",

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TY - JOUR

T1 - Nature of the Ru−NO Coordination Bond

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

UR - https://www.scopus.com/pages/publications/85016989173

U2 - 10.1002/open.201700028

DO - 10.1002/open.201700028

M3 - Article

AN - SCOPUS:85016989173

SN - 2191-1363

VL - 6

SP - 410

EP - 416

JO - ChemistryOpen

JF - ChemistryOpen

IS - 3

ER -

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

Abstract

Keywords

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