Nitrido-ruthenium(VI) and -osmium(VI) complexes containing chelating multianionic (N, O) ligands. Synthesis, crystal structures and reactions with triphenylphosphine

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Pui-Ming Chan, Wing-Yiu Yu, Chi-Ming Che and Kung-Kai Cheung


Abstract

A series of nitrido-ruthenium(VI) and -osmium(VI) complexes containing chelating di-, tri- and tetra-anionic ligands was synthesized by ligand substitution reaction in methanol under room conditions in the presence of 2,6-dimethylpyridine. All the newly prepared complexes are air-stable diamagnetic solids. The crystal structures of seven complexes have been established by X-ray crystallography. The Ru[triple bond, length half m-dash]N (1.615–1.594 Å) and the Os[triple bond, length half m-dash]N (1.612–1.621 Å) bond distances are rather insensitive to the electron-donating power of the auxiliary ligands. All the nitridoruthenium(VI) complexes react spontaneously with triphenylphosphine, and the intermediate [RuIV(N[double bond, length half m-dash]PPh3)L1(py)Cl] has been isolated and characterized spectroscopically for the reaction with [RuVIN(L1)Cl]. However, for those nitridoruthenium(VI) complexes bearing the tri- (L2)3– and tetra-anionic (L3,4)4– ligands, the phosphiniminatoruthenium(IV) intermediate undergoes further reaction with pyrazole to generate a bis(pyrazole)ruthenium(IV) complex as the product.


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