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Abstract

Electrochemical reduction of the triangular clusters [Os₃(CO)₁₀(α-diimine)] (α-diimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os₃(CO)₁₀(μ-bpym)ReBr(CO)₃] produces primarily the corresponding radical anions. Their stability is strongly determined by the π-acceptor ability of the reducible α-diimine ligand, which decreases in the order μ-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(α-diimine) chelate ring causes weakening of the axial (CO)₄Os-Os(CO)₂(α-diimine) bond and its facile cleavage for α-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest π-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re(bpym) chelate bond, the Os₃-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os₃(CO)₁₀(bpym)]^•- at T = 223 K gives the open-triosmium core (= Os₃*) dianion, [Os₃*(CO)₁₀(bpym)]^2-. Its oxidation leads to the recovery of parent [Os₃(CO)₁₀(bpym)]. At room temperature, [Os₃*(CO)₁₀(bpym)]^2- is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open-core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os₃*(CO)₁₀(bpym)]^2- rapidly attacks yet non-reduced parent cluster molecules, producing the relatively stable open-core dimer [Os₃*(CO)₁₀(bpym)]₂^2- featuring two open-triangle cluster moieties connected with an (bpym)Os-Os(bpym) bond. In butyronitrile, [Os₃*(CO)₁₀(bpym)]^2- is stabilised by the solvent and the dimer [Os₃*(CO)₁₀(bpym)]₂^2- is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os₃(CO)₁₀(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os₃*(CO)₁₀(α-diimine)]₂^2-. The products formed are [Os₂(CO)₈]^2- and {Os(CO)₂(α-diimine)}₂. The latter dinuclear fragments constitute a linear polymeric chain [Os(CO)₂(α-diimine)]_n that is further reducible at the α-diimine ligands. For α-diimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os₃(CO)₁₀(α-diimine)] clusters exhibits several common features with their photochemistry. The same Os-α-diimine bond dissociates in both cases but the intimate mechanisms are different.

Keywords: Osmium clusters; α-Diimine ligands; Electrochemical reduction; Spectroelectrochemistry; Cyclic voltammetry; Organometallic polymers; Zwitterions; IR spectroscopy; Photochemistry.

References: 55 live references.