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Shedding light on the electronic structure of [Ru(η6-C16H16)(NH3)3]2+ complex: a computational insight

  • Renato P. OrenhaEmail author
  • Giovanni F. Caramori
  • Alechania Misturini
  • Sérgio E. Galembeck
Original Paper
  • 150 Downloads
Part of the following topical collections:
  1. VII Symposium on Electronic Structure and Molecular Dynamics – VII SeedMol

Abstract

Ruthenophanes have been recognized as potential candidates to the design of electrically conducting polymers, particularly due to their electrochemical, structural, and spectroscopic properties. The comprehension and rationalization of the metal–ligand interaction is fundamental to pave the way for future applications as the design of new conducting materials. For that reason, this investigation sheds light on the electronic details behind the cation–π interactions present in ruthenophanes by using [Ru(η6-C16H16)(NH3)3]2+ as a model. Zeroth-order symmetry-adapted perturbation theory (SAPT0) shows the interaction Ru(II)–[2.2]paracyclophane with a predominant covalent character. However, the hapticity analysis of [2.2]paracyclophane shows only two predominantly covalent Ru–C bonds, as highlighted by the total energy density, H(r), in the bond critical point (BCP) obtained from quantum theory of atoms in molecules (QTAIM) method, and by second-order stabilization energy, ΔE(2), related to the processes: π C–C → dσ or dπ Ru, achieved in the natural bond orbital (NBO) method. The other two Ru–C chemical bonds show a largely electrostatic character, as can be visualized from the delocalization index, DI, between the electron basins in the electron localization function (ELF) method. Remarkably, the interacting quantum atoms (IQA) method showed practically the same value of the total interaction energy, E\(_{\text {int} }^{\text {AB}}\), between Ru and these C atoms and, then, corroborates the hapticity four of the ligand: [2.2]paracyclophane. Source function distribution presents a correlation with the electronic interactions between different groups in [Ru(η6-C16H16)(NH3)3]2+.

Graphical Abstract

The nature of the interactions between [Ru(NH3)3]2+ and [2.2]paracyclophane in [Ru(η6-C16H16)(NH3)3]2+ was investigated with different methods of energy decomposition and electron density analysis. This interaction has a predominantly covalent character. It was possible to observe that some Ru-C interactions have a larger covalent character, in contrast for other that are mainly ionic.

Keywords

Cation–π interaction SAPT Ru-C chemical bond ELF Hapticity IQA 

Notes

Acknowledgements

The authors thank the Brazilian agencies Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Programa de Apoio à Pós-Graduação (PROAP), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) (Grant 304447/2010-2), and São Paulo Research Foundation (FAPESP, Fundação de Amparo à Pesquisa do Estado de São Paulo) (Grants 2008/02677-0 and 2014/5026 5-3) for financial support. SEG thanks CNPq for research fellowships (Grants 304393/2013-4 and 308254/2016-3). RPO thanks FAPESP for graduate fellowships (Grants 2011/20351-7 and 2015/15176-2). GFC thanks CNPq (Grant 311963/2017-0) for the research fellowship and the Centro Nacional de Supercomputação CESUP-UFRGS for the excellent computational service provided. We also acknowledge Ali Faez Taha for technical assistance.

Supplementary material

894_2018_3882_MOESM1_ESM.pdf (792 kb)
(PDF 791 KB)

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Authors and Affiliations

  1. 1.Departamento de Química, FFCLRPUniversidade de São PauloRibeirão PretoBrazil
  2. 2.Departamento de QuímicaUniversidade Federal de Santa Catarina, Campus Universitário TrindadeFlorianópolisBrazil

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