Diruthenium and triruthenium compounds of the potential redox active non-chelated η1-N,η1-N-benzothiadiazole bridge

Abstract

In the present study, a series of non-chelated BTD (2,1,3-benzothiadiazole)-bridged diruthenium(II) ([{(CH₃CN)(acac)₂Ru^II}₂(μ-BTD)] 1, [{CH₃CN(acac)₂Ru^II}(μ-BTD){Ru^II(acac)₂(η¹-N-BTD)}] 2, [{(η¹-N-BTD)(acac)₂Ru^II}₂(μ-BTD)] 3), and triruthenium ([{(acac)₂Ru^II}₃(μ-BTD)₂(η¹-N-BTD)₂] 4) complexes with varying ratios of η¹-N and μ-bis-η¹-N,η¹-N modes of BTD were studied. Complexes 1–4 (S = 0) were obtained via the one-pot reaction of electron-rich Ru(acac)₂(CH₃CN)₂ and electron-deficient BTD in refluxing acetone. The relatively low Ru(II)/Ru(III) potential of 1–4 (0.08–0.44 V versus SCE) further facilitated the isolation of the corresponding mixed valent Ru^IIRu^III (S = 1/2) and Ru^IIRu^IIRu^III (S = 1/2)/Ru^IIRu^IIIRu^III (S = 1) forms [1]ClO₄–[3]ClO₄ and [4]ClO₄/[4](ClO₄)₂, respectively. The single-crystal X-ray structures of the representative mixed valent [1]ClO₄ and [3]ClO₄ established (i) Ru⋯Ru distances of 6.227 Å and 6.256 Å (molecule A)/6.184 Å (molecule B), respectively, (ii) a significant variation of the N–S distance of BTD in [3]ClO₄ as a function of its binding mode μ versus η¹ and (iii) similar Ru–N (μ-BTD) distances in each case corresponding to a valence delocalised situation. The mixed valent diruthenium (1⁺–3⁺) and triruthenium (4⁺/4²⁺) complexes exhibited metal-based anisotropic electron paramagnetic resonance (EPR) and moderately intense low-energy intervalence charge-transfer (IVCT) transitions in the near-infrared region of 1730–1890 nm. Analysis of the IVCT band using the Hush treatment revealed a valence delocalised class III mixed valent state with the electronic coupling V_ab of ≈2640–2890 cm⁻¹, as also corroborated by the K_c values of 10⁵–10⁸, solvent independency of the IVCT band and uniform spin distribution between the metal ions in the singly occupied state(s). Furthermore, the involvement of the BTD (η¹ and μ)-based orbitals in the reduction processes was evident by its free radical EPR feature.