Structural, spectroscopic and electronic properties of a family of face-shared bi-octahedral Ru25+/6+ complexes with a bridging 2,5-di(2-pyridyl)pyrrolide ligand

Shi-Rui Kang; Zi-Qin Zhou; Chang-Feng Xiong; Bin Liu; John E. McGrady; Mohammed Obies; Chao Liu; Piao He; Xiao-Yi Yi

doi:10.1039/D0DT01325K

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Structural, spectroscopic and electronic properties of a family of face-shared bi-octahedral Ru₂^5+/6+ complexes with a bridging 2,5-di(2-pyridyl)pyrrolide ligand†

Shi-Rui Kang,^a Zi-Qin Zhou,^b Chang-Feng Xiong,^a Bin Liu,

*^b John E. McGrady,

*^c Mohammed Obies,^cd Chao Liu,

^a Piao He

^a and Xiao-Yi Yi

*^a

Author affiliations

* Corresponding authors

^a College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, P. R. China
E-mail: xyyi@csu.edu.cn

^b A key Laboratory of Synthetic and Natural Function Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, P. R. China
E-mail: liubin@nwu.edu.cn

^c Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UK
E-mail: john.mcgrady@chem.ox.ac.uk

^d College of Pharmacy, University of Babylon, Hilla, Iraq

Abstract

A family of Ru₂ dimers, [Ru₂(μ-κ₂N,N′:κ₂N′,N′′-dpp)₂(μ-X)(X)₂]^q+ (X = Cl, Br, q = 0 and X = I, q = 1) is synthesized from a [Ru₂(OAc)₄Cl] paddlewheel starting material. The neutral products are mixed-valence Ru₂⁵⁺ dimers with a Ru–Ru bond order of 0.5, while the cationic iodide is a Ru₂⁶⁺ dimer with formal bond order of 1.0. The Ru–Ru distance is strikingly independent of the identity of the halide and the oxidation state of ruthenium, most likely a consequence of the small bridging nitrogen which constrains the geometry. The spectroscopic properties (EPR, UV/Vis) of the Br complex are consistent with a large σ–σ* splitting in [Ru₂(μ-κ₂N,N′:κ₂N′,N′′-dpp)₂(μ-Br)(Br)₂].

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Article information

DOI: https://doi.org/10.1039/D0DT01325K
Article type: Paper
Submitted: 10 Apr 2020
Accepted: 05 May 2020
First published: 05 May 2020

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Dalton Trans., 2020,49, 7053-7059

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Structural, spectroscopic and electronic properties of a family of face-shared bi-octahedral Ru₂^5+/6+ complexes with a bridging 2,5-di(2-pyridyl)pyrrolide ligand

S. Kang, Z. Zhou, C. Xiong, B. Liu, J. E. McGrady, M. Obies, C. Liu, P. He and X. Yi, Dalton Trans., 2020, 49, 7053 DOI: 10.1039/D0DT01325K

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