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- W1989905359 abstract "The oxidation of [Os(NH3)5Cl]2+ by CeIV in water gave [OsN(NH3)4]3+ quantitatively. Excitation of [OsN(NH3)4]3+ in the solid state or in solution at 300–400 nm resulted in room-temperature photoluminescence. The low-lying spin orbital E sublevel of the 3E {3[(dxy)1(dπ*)1]} state was assigned as the emission state. The excited state of [OsN(NH3)4]3+ was quenched by electron donors such as aromatic hydrocarbons, alkoxybenzenes, amines and alcohols. A photoinduced electron-transfer mechanism is proposed for the quenching processes. The emission lifetime of [OsN(NH3)4]3+ depended on the complex concentration. An excited-state bimolecular self-quenching mechanism ([OsVIN]*+[OsVIN]→ product) is likely. Photolysis of [OsN(NH3)4]3+ in the presence of an electron donor such as 1,4-dimethoxybenzene or C6Me6 in acetonitrile led to the formation of the µ-dinitrogen product [{Os(NH3)4(CH3CN)}2N2]5+. The coupling reaction obeyed the kinetics rate =k2[OsVI][OsV] where k2 was estimated to be (3.75 ± 0.30)× 105 dm3 mol–1 s–1 at 298 K. Oxidation of [{Os(NH3)4–(CH3CN)}2N2]5+ by CeIV in water followed by precipitation with 2 mol dm–3 HCl gave the product [OsN(NH3)4]Cl3 in detectable yield." @default.
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- W1989905359 date "1992-01-01" @default.
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- W1989905359 title "Photoredox properties of [OsN(NH3)4]3+ and mechanism of formation of [{Os(NH3)4(CH3CN)}2N2]5+ through a nitrido-coupling reaction" @default.
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- W1989905359 doi "https://doi.org/10.1039/dt9920001411" @default.
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