A Ru diphosphonato complex with a metal-metal bond for water oxidation.

Unlike [Ru2(µ-O2CCH3)4], the structurally analogous water-soluble RuII,III2 diphosphonato complex K3[Ru2(hedp)2(H2O)2] (K3·1) is only involved in stoichiometric water oxidation with a maximum 67% O2 yield under CAN/HNO3 solution (pH 1.0) for 2.5 h. The water oxidation mechanism and intermediate products were ascertained by UV-vis, ESI-MS and DFT calculation.

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.

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].

Reversible pyrrole-based proton storage/release in ruthenium(ii) complexes.

Newly designed ruthenium(ii) complexes are reported which contain a pyridylpyrrole ligand featuring fast-responsive and reversible proton storage/release on the pyrrole group. The protonated pyrrolium acts as an acidic initiator and is capable of triggering the polymerization of 2,2-dimethyloxirane.