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 |
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Pages (from-to) | 410-416 |
Number of pages | 7 |
Journal | ChemistryOpen |
Volume | 6 |
Issue number | 3 |
DOIs | |
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 |
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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