Structural and electronic forms of doubly oxido/Pz and triply oxido/(Pz)2 bridged mixed valent and isovalent diruthenium complexes (Pz = pyrazolate)

Abstract

The article reported on the diastereomeric dinuclear mixed-valent complexes [(acac)₂Ru(III)(μ-O)(μ-Pz^R)Ru(IV)(acac)₂] (R = H, Me, meso: ΔΛ, 1a–1c; rac: ΔΔ/ΛΛ, 2a–2c) and rac-[(acac)₂Ru(III)(μ-O)(μ-Iz)Ru(IV)(acac)₂], (2d) (HPz = pyrazole, HIz = indazole, acac = acetylacetonate). Moreover, the diruthenium(II,II) complexes [(HPz)₃Ru(II)(μ-O)(μ-Pz)₂ Ru(II)(HPz)₃] (3a) and [(HIz)₃Ru(II)(μ-O)(μ-Iz)₂Ru(II)(HIz)₃] (3d) were presented. The analogous form of 3a, i.e., [(HPz)₂(Pz)Ru(III)(μ-O)(μ-Pz)₂Ru(III)(Pz)(HPz)₂], was previously reported. Single crystal X-ray structures of 1a–1c/2a–2d and representative 3a showed their molecular forms, including the diastereomeric nature of the former. The Ru–O–Ru angle decreased appreciably on switching from doubly bridged 1 and 2 (128–135°) to triply bridged 3a (114°). Both series of complexes displayed rhombic symmetry in their EPR spectra, with g₁ and g₂ being very similar for 1a–1c with an almost axial look. The mixed-valence complex with a Ru(III)Ru(IV) (S = 1/2) state of 1 and 2 would lead to iso-valence complexes of Ru(III)Ru(III) and Ru(IV)Ru(IV) with an EPR inactive state by one electron redox reaction. On the other hand, metal based {Ru(II)Ru(II)/Ru(II)Ru(III), 3a/3a⁺} and terminal ligand (HPz/HPz⁻, 3a/3a⁻) based redox processes displayed anisotropic and free radical EPR, respectively. An IVCT (intervalence charge transfer) band was found for the delocalised mixed valent 1 and 2 {Ru(III)Ru(IV)} or 3a⁺ {Ru(II)Ru(III)} in the NIR region. The intense metal-to-ligand charge transfer (MLCT) transitions of 1–3 in the visible region varied systematically as a function of the metal oxidation state.