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A low-valent dinuclear ruthenium diazadiene complex catalyzes the oxidation of dihydrogen and reversible hydrogenation of quinones.

Chemical Science 2019 January 29
The dinuclear ruthenium complex [Ru2 H(μ-H)(Me2 dad)(dbcot)2 ] contains a 1,4-dimethyl-diazabuta-1,3-diene (Me2 dad) as a non-innocent bridging ligand between the metal centers to give a [Ru2 (Me2 dad)] core. In addition, each ruthenium is bound to one dibenzo[ a , e ]cyclooctatetraene (dbcot) ligand. This Ru dimer converts H2 to protons and electrons. It also catalyzes reversibly under mild conditions the selective hydrogenation of vitamins K2 and K3 to their corresponding hydroquinone equivalents without affecting the C[double bond, length as m-dash]C double bonds. Mechanistic studies suggest that the [Ru2 (Me2 dad)] moiety, like hydrogenases, reacts with H2 and releases electrons and protons stepwise.

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