Issue 40, 2009

Low-valence oxo-centred triruthenium complexes by bridging acetate substitution with pyrazolyldiazine or pyridinyltetrazine ligands

Abstract

A series of oxo-centred triruthenium-acetate complexes with valence III,III,II were prepared by reactions of [Ru3III,III,III]+ precursor [Ru3O(OAc)6(py)2(CH3OH)]+ (1) with 3-chloro-6-(pyrazol-1-yl)pyridazine (cppd), 3-chloro-6-(3,5-dimethylpyrazol-1-yl)pyridazine (cmppd), 3,6-bis(pyrazol-1-yl)pyridazine (ppd), 3,6-bis(3,5-dimethylpyrazol-1-yl)pyridazine (mppd) or 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz). When neutral Ru3III,III,II precursor Ru3O(OAc)6(CO)(CH3OH)2 (2) was utilized, a stable low-valence Ru3III,II,II derivative complex was successfully isolated. As established through crystal structural analyses, they were derived from 1 or 2 by substitution of the axial methanol and one of six bridging acetates in the parent Ru33-O)(μ-OAc)6 cluster core as well as one axial pyridine in some cases. As revealed by electrochemical and spectroscopic studies, substituting one of the six bridging acetates in the parent Ru33-O)(μ-OAc)6 cluster core significantly modifies the electronic and redox characteristics. Compared with those for the parent compound [Ru3O(OAc)6(py)3]+, triruthenium-based redox potentials of these derivatives show remarkable positive shifts.

Graphical abstract: Low-valence oxo-centred triruthenium complexes by bridging acetate substitution with pyrazolyldiazine or pyridinyltetrazine ligands

Supplementary files

Article information

Article type
Paper
Submitted
05 May 2009
Accepted
14 Aug 2009
First published
27 Aug 2009

Dalton Trans., 2009, 8696-8703

Low-valence oxo-centred triruthenium complexes by bridging acetate substitution with pyrazolyldiazine or pyridinyltetrazine ligands

F. Dai, H. Ye, B. Li, L. Zhang and Z. Chen, Dalton Trans., 2009, 8696 DOI: 10.1039/B908798B

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