A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex

Three new diruthenium oxyanion complexes have been prepared, crystallographically characterized, and screened for their potential to photochemically unmask a reactive Ru—Ru═O intermediate. The most promising candidate, Ru2(chp)4ONO2 (4, chp = 6-chloro-2-hydroxypyridinate), displays a set of signals centered around m/z = 733 amu in its MALDI-TOF mass spectrum, consistent with the formation of the [Ru2(chp)4O]+ ([6]+) ion. These signals shift to 735 amu in 4*, which contains an 18O-labeled nitrate. EPR spectroscopy and headspace GC-MS analysis indicate that NO2• is released upon photolysis of 4, also consistent with the formation of 6. Photolysis of 4 in CH2Cl2 at room temperature in the presence of excess PPh3 yields OPPh3 in 173% yield; control experiments implicate 6, NO2•, and free NO3– as the active oxidants. Notably, Ru2(chp)4Cl (3) is recovered after photolysis. Since 3 is the direct precursor to 4, the results described herein constitute the first example of a synthetic cycle for oxygen atom transfe...