Reactions of dimesityldioxo-osmium(VI) with donor ligands; reactions of MO2(2,4,6-Me3C6H2)2, M = Os or Re, with nitrogen oxides. X-Ray crystal structures of [2,4,6-Me3C6H2N2]+[OsO2(ONO2)2(2,4,6-Me3C6H2)]–, OsO(NBut)(2,4,6-Me3C6H2)2, OsO3(NBut), and ReO3[N(2,4,6-Me3C6H2)2]

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Abstract
The interaction of OsO2(mes)2(mes = 2,4,6-Me3C6H2), with pyridines, an isocyanide, and tertiary phosphines gives rise to complexes such as trans-OsO2(bipy)(mes)2(bipy = 2,2′-bipyridyl), cis-OsO2(2,6-Me2C6H3NC)(mes)2, and cis-OsO2(PR3)2(mes)2. The oxoimido compound, OsO(NBut)(mes)2, has been synthesised. The reactions of MO2(mes)2, M = Os or Re, with oxides of nitrogen, which involve oxygen transfer to the metal atom, have been studied. With NO, ReO2(mes)2 gives the dimesitylamido compound, ReO3[N(mes)2], but OsO2(mes)2 is unreactive. The compound ReO2(mes)2 reacts with NO2(N2O4) quantitatively to give ReO3(mes), nitromesitylene, and 2,4,6-trimethylbenzenediazonium nitrate, OsO2(mes)2 gives the salt [(mes)N2]+[OsO2(ONO2)2(mes)] together with nitromesitylene and NO. The X-ray crystal structures of four compounds have been determined. In [(mes)N2][OsO2(ONO2)2(mes)] the anion has a distorted trigonal-bipyramidal structure with equatorial oxo functions and the unidentate O-bonded nitrates axial. The compounds OsO(NBut)(mes)2 and OsO3(NBut) are distorted tetrahedral with essentially linear, 4e imido ligands. The compound ReO3[N(mes)2] is also distorted tetrahedral and in the solid state shows evidence of ReO ⋯ Me(mes) interactions.