Ru(IV)-Ru(IV), Ru(III)-Ru(IV), and Ru(III)-Ru(III) complexes having a sulfato bridging ligand on the doubly oxido-/hydroxido-bridged core, and their crystallographic and electronic structures.

The Ru(IV,IV), Ru(III,IV), and Ru(III,III) complexes with the doubly oxido- and/or hydroxido-bridged diamond core {Ru(μ-O(H))}, bridged by an η:η:μ-type bidentate sulfato ligand, [{Ru(L)}(μ-O)(μ-OSO)] ( = 1: [III,IV]; = 2: [IV,IV]), [{Ru(L)}(μ-O)(μ-OH)(μ-OSO)] ([III,IV_1H]), and [{Ru(L)}(μ-OH)(μ-OSO)] ([III,III_2H]) (L = ethylbis(2-pyridylmethyl)amine), were synthesised as ClO-salts, and their crystal and electronic structures investigated. The corresponding hydrogencarbonato-bridged Ru(III,III) complex, [{Ru(L)}(μ-OH)(μ-OCOH)] ([III,III(HCO3)_2H]), was also prepared and its crystallographic and electronic structures compared to those of the sulfato-bridged system, [III,III_2H]. All the sulfato-bridged complexes isolated were confirmed in the Pourbaix diagram, wherein the redox potential was plotted as a function of pH.

Synthesis of Carbonato- and Doubly Oxido-Bridged Diruthenium(III,IV) Complex and Reactions with Cations.

Doubly oxido-bridged transition metal moieties, {M(μ-O)}, play important roles as oxidation reaction centers in nature. This work features a diruthenium(III,IV) complex with a doubly oxido-bridged core {Ru(μ-O)} with a carbonato bridged between the two ruthenium centers, M[{Ru(ebpma)}(μ-O)(μ-OCO)](PF) (M[](PF); , ebpma; ethylbis(2-pyridymethyl)amine), and explores the interactions of this complex with cations (H and M). M[](PF) was formed via reactions of a singly oxido-bridged complex, [{RuCl(ebpma)}(μ-O)]PF(CH)CO, with MCO (M = K, Na) or with CO(), adjusted to around pH 12 with NaOH(aq.