Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry and Computational Investigation of [Ru6C(CO)15]4–

The reaction of [Ru6C(CO)16]2− (1) with NaOH in DMSO resulted in the formation of a highly reduced [Ru6C(CO)15]4− (2), which was readily protonated by acids, such as HBF4·Et2O, to [HRu6C(CO)15]3− (3). Oxidation of 2 with [Cp2Fe][PF6] or [C7H7]- [BF4] in CH3CN resulted in [Ru6C(CO)15(CH3CN)]2− (5), which was quantitatively converted into 1 after exposure to CO atmosphere. The reaction of 2 with a mild methylating agent such as CH3,I afforded the purported [Ru6C(CO)14(COCH3)]3− (6). By employing a stronger reagent, that is, CF3SO3CH3, a mixture of [HRu6C(CO)16]− (4), [H3Ru6C(CO)15]− (7), and [Ru6C(CO)15(CH3CNCH3)]− (8) was obtained. The molecular structures of 2−5, 7, and 8 were determined by single-crystal X-ray diffraction as their [NEt4]4[2]·CH3CN, [NEt4]3[3], [NEt4][4], [NEt4]2[5], [NEt4][7], and [NEt4][8]·solv salts. The carbyne−carbide cluster 6 was partially characterized by IR spectroscopy and ESI-MS, and its structure was computationally predicted using DFT methods. The redox behavior of 2 and 3 was investigated by electrochemical and IR spectroelectrochemical methods. Computational studies were performed in order to unravel structural and thermodynamic aspects of these octahedral Ru− carbide carbonyl clusters displaying miscellaneous ligands and charges in comparison with related iron derivatives.