Reduction of iridocenium salts [Ir(eta(5)-C5Me5)(eta(5)-L)](+) (L=C5H5, C5Me5, C9H7); Ligand-to-ligand dimerisation induced by electron transferстатья
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Аннотация:Redox properties of iridium complexes [Ir(eta(5)-C5Me5)(eta(5)-L)](+) (1(+), L = C5H5; 2(+), L = C5Me5; 3(+), L = C9H7) were studied by cyclic voltammetry (CV). All three complexes can be reduced to 19-electron radicals 1-3. The stability and reactivity of these radicals depend on the electronic and steric properties of the ligands. The mixture of dimers [(eta(5)-C5Me5)Ir(mu-eta(4):eta(4)-C5H5C5Me5)Ir(eta(5)-C5H5)] (4a) and [(eta(5)-C5H5)Ir(mu-eta(4):eta(4)-C5Me5C5Me5)Ir(eta(5)-C5H5)] (4b) was formed as a result of reduction of 1(+) with Na/Hg in THF. Both chemical and electrochemical reduction of 2(+) gave the dimer [(eta(5)-C5Me5)Ir(mu-eta(4):eta(4)-C5Me5C5Me5)lr(eta(5)-C5Me5)] (5) in low yield. Reduction of 3(+) gave the tetranuclear complex [(eta(5)-C5Me5)Ir(mu-eta(4):eta(5)-C9H7)Ir(mu-eta(4):eta(4)-C5Me5C5Me5)Ir(mu-eta(5):eta(4)-C9H7)Ir(eta(5)-C5Me5)] (6).