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

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

Dalton Trans. 2020 Jun 2;49(21):7053-7059. doi: 10.1039/d0dt01325k.

Authors

Shi-Rui Kang¹, Zi-Qin Zhou², Chang-Feng Xiong¹, Bin Liu², John E McGrady³, Mohammed Obies⁴, Chao Liu¹, Piao He¹, Xiao-Yi Yi¹

Affiliations

¹ College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, P. R. China. xyyi@csu.edu.cn.
² 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. liubin@nwu.edu.cn.
³ Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UK. john.mcgrady@chem.ox.ac.uk.
⁴ Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QZ, UK. john.mcgrady@chem.ox.ac.uk and College of Pharmacy, University of Babylon, Hilla, Iraq.

PMID: 32400777
DOI: 10.1039/d0dt01325k

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].