Bonding interactions between sulfur dioxide (SO2) and mono-ruthenium(II)-substituted Keggin-type polyoxometalates: electronic structures of ruthenium–SO2 adducts

Bo Zhu; Zhong-Ling Lang; Na-Na Ma; Li-Kai Yan; Zhong-Min Su

doi:10.1039/C4CP01389A

Bonding interactions between sulfur dioxide (SO₂) and mono-ruthenium(ii)-substituted Keggin-type polyoxometalates: electronic structures of ruthenium–SO₂ adducts

Bo Zhu,^a Zhong-Ling Lang,

^a Na-Na Ma,^a Li-Kai Yan*^a and Zhong-Min Su*^a

Author affiliations

* Corresponding authors

^a Institute of Functional Material Chemistry, Faculty of Chemistry, Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun 130024, P. R. China
E-mail: yanlk924@nenu.edu.cn, zmsu@nenu.edu.cn
Fax: +86-431-85684009

Abstract

Density functional theory (DFT) calculations and natural bond orbital (NBO) analysis were carried out to investigate the electronic structures and bonding features between the ruthenium(II) atom and the SO₂ molecule in two ruthenium–sulfur dioxide (SO₂) adducts, trans-Ru(NH₃)₄(SO₂)Cl⁺ and [{SiW₁₁O₃₉}Ru^II(SO₂)]⁶⁻. In addition, the bonding interactions between SO₂ and the metal-ruthenium fragment were determined by binding energy (ΔE_abs) calculation and electronic structures. The results indicate that the η¹-S-planar model in both trans-Ru(NH₃)₄(SO₂)Cl⁺ and [{SiW₁₁O₃₉}Ru^II(SO₂)]⁶⁻ are more favorable. NBO analysis of the bonding interaction between ruthenium and sulfur centers in the [{SiW₁₁O₃₉}Ru^II(SO₂)]⁶⁻ complex shows that it possesses a σ and a π bond. It predicts that the polyoxometalate [SiW₁₁O₃₉Ru]⁶⁻ can serve as a potential adsorbent for the SO₂ molecule because of the strong Ru–S bond relative to Ru(NH₃)₄Cl⁺.

Article information

https://doi.org/10.1039/C4CP01389A

Article type

Paper

Submitted

31 Mar 2014

Accepted

08 Jul 2014

First published

14 Jul 2014

Download Citation

Phys. Chem. Chem. Phys., 2014,16, 18017-18022

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Bonding interactions between sulfur dioxide (SO₂) and mono-ruthenium(II)-substituted Keggin-type polyoxometalates: electronic structures of ruthenium–SO₂ adducts

B. Zhu, Z. Lang, N. Ma, L. Yan and Z. Su, Phys. Chem. Chem. Phys., 2014, 16, 18017 DOI: 10.1039/C4CP01389A

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