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. 2016 Aug 10;138(31):10032-40.
doi: 10.1021/jacs.6b05942. Epub 2016 Jul 28.

A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex

Amanda R Corcos  1 , József S Pap  1 , Tzuhsiung Yang  1 , John F Berry  1
Affiliations

A Synthetic Oxygen Atom Transfer Photocycle from a Diruthenium Oxyanion Complex

Amanda R Corcos et al. J Am Chem Soc. .

Abstract

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 (18)O-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 transfer that makes use of light to generate a putative metal oxo intermediate.

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Conflict of interest statement

Notes

The authors declare no competing financial interests.

Figures

Figure 1
Figure 1
Thermal ellipsoid plot of 4•2CH2Cl2 with ellipsoids drawn at the 50% probability level. Hydrogen atoms and molecules of solvation are omitted for clarity.
Figure 2
Figure 2
Thermal ellipsoid plot of 5•2CH2Cl2 with ellipsoids drawn at the 50% probability level. Hydrogen atoms and molecules of solvation are omitted for clarity.
Figure 3
Figure 3
UV/Vis for compounds 3-5 in CH2Cl2. The spectrum for 3 was previously reported but is included here for direct comparison.
Figure 4
Figure 4
Cyclic voltammograms of Ru25/4+ couple for 3-5 versus Fc/Fc+. E1/2 for each species is marked with a dashed vertical line.
Figure 5
Figure 5
MALDI-TOF mass spectrum for 4 (black, top). Simulation (red) indicates isotope pattern at m/z = 733 amu is due to [Ru2(chp)4O]+. Upon isotopic labeling, MALDI-TOF mass spectrum for 4* (black, below) shifts by 2 units, as confirmed by simulation (red, bottom).
Figure 6
Figure 6
EPR spectrum and simulation of 4 recorded at 10 K.
Figure 7
Figure 7
EPR spectrum of 4 in CH2Cl2 taken at 10 K after 16 hours of frozen photolysis using 254 nm light. Inset: simulations of NO3• (blue, above) and NO2• (red, middle) compared to 4 after frozen photolysis (black, below).
Figure 8
Figure 8
GC-MS headspace analysis for the formation of N18O2• (m/z = 50) after photolysis of 4* at room temperature under N2 for 4 hours using 350 nm wavelength light. As compared to the counts for m/z = 50 amu for the N2 control, N18O2• is clearly formed under reaction conditions.
Figure 9
Figure 9
Yield of OPPh3 after exposure to different oxygen atom sources, both with and without exposure to photolytic conditions.
Scheme 1
Scheme 1
Formation of mononuclear metal nitride and oxo species after exposure of metal azides and oxyanions to light, respectively.
Scheme 2
Scheme 2
Possible stoichiometric cycle illustrating the synthetic limitations of current oxyanion systems.
Scheme 3
Scheme 3
Formation of nitrate complex 2 from chloride precursor 1 and oxyanion complexes 4 and 5 from chloride precursor 3.
Scheme 4
Scheme 4
Possible products upon exposing nitrate complexes to photolytic conditions.
Scheme 5
Scheme 5
Proposed mechanistic scheme for the oxygen atom transfer reaction presented here. Proposed intermediates 6 and Ru2(chp)4 are in dashed boxes.
See this image and copyright information in PMC

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