Synthesis and Characterization of Ru<sub>2</sub>(DMBA)<sub>4</sub>X<sub>2</sub> (X = CN, N<sub>3</sub>, N(CN)<sub>2</sub>, I): Controlling Structural, Redox, and Magnetic Properties with Axial Ligands
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Metathesis reactions between Ru2(DMBA)4Cl2 (DMBA = N,N‘-dimethylbenzamidinate) and MX (M = Na and K) yielded bis-adduct derivatives Ru2(DMBA)4X2 (X = CN (1), N3 (2), N(CN)2 (3)). Metathesis reactions between Ru2(DMBA)4(NO3)2 and KI resulted in Ru2(DMBA)4I2 (4). Compound 1 is diamagnetic, while compounds 2−4 are paramagnetic (S = 1). Both compounds 1 and 2 undergo two reversible one-electron processes, an oxidation and a reduction, while compound 3 features a quasireversible reduction. Single-crystal X-ray diffraction studies revealed that the Ru−Ru bond lengths are 2.4508(9), 2.3166(7), 2.304[1], and 2.328(1) Å for compounds 1−4, respectively. Structural and electrochemical data clearly indicate that the axial ligands impart a significant influence on the electronic structures of diruthenium species.
