Ru(Iv)-Ru(Iv) complexes having the doubly oxido-bridged core with a bridging carbonato or hydrogencarbonato ligand

Ru(iv)-Ru(iv) complexes having the doubly oxido-bridged diamond core with a bridging carbonato or hydrogencarbonato ligand, [{Ru-IV(ebpma)}(2)(mu-O)(2)(mu-O2CO(H)(m))]X-n (ebpma; ethylbis(2-pyridylmethyl)amine, m = 0; [IV,IV]X-2 (X = PF6, ClO4), m = 1; [IV,IV_1H](ClO4)(3)), were isolated via the oxidation of the corresponding carbonato-bridged Ru(iii)-Ru(iv) complex ([III,IV](+)), and [IV,IV](ClO4)(2) and [IV,IV_1H](ClO4)(3) were structurally characterized. The electrochemical and spectroscopic properties of [IV,IV](2+) and [IV,IV_1H](3+) were investigated both in organic solvents and aqueous solutions. The reactivity toward organic solvents having (a) methyl group(s) and reactions with organic substrates were studied as well. This should be the first time when systematic comparisons of the Ru(iv)-Ru(iv) species and corresponding Ru(iii)-Ru(iv) complexes in the same tridentate ligand system were made.

Automated summary

Ru(iv)-Ru(iv) complexes with a doubly oxido-bridged diamond core and bridging carbonate or hydrogen carbonate ligands were synthesized from the corresponding carbonato-bridged Ru(iii)-Ru(iv) complex. The structures of [IV,IV](ClO4)(2) and [IV,IV_1H](ClO4)(3) were characterized. The electrochemical and spectroscopic properties of [IV,IV](2+) and [IV,IV_1H](3+) in organic solvents and aqueous solutions, as well as their reactivity towards organic solvents and substrates, were investigated. This is the first systematic comparison of Ru(iv)-Ru(iv) species and corresponding Ru(iii)-Ru(iv) complexes in the same tridentate ligand system.