Metal–oxo photo-oxidants. Photochemistry and photophysics of trans-[OsVI(tmc)(O)2]2+(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[OsVI(CN)4(O)2]2–

Abstract
trans-[OsVI(tmc)(O)2]2+(tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane) and trans-[OsVI(CN)4(O)2]2– are emissive in the solid state and in fluid solutions at room temperature (τ∼ 1.0–1.5 µs); the 3Eg state of trans-[OsVI(tmc)(O)2]2+ is a powerful one-electron oxidant {[OsVI(O)2]2++ e→[OsV(O)2]+, Ef 0 > 2.0 V vs. normal hydrogen electrode} in aqueous solution, reacting with PPh3 and (PhCH2)2S to give OPPh3 and (PhCH2)2SO, respectively.

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