Journal
CATALYSIS TODAY
Volume 310, Issue -, Pages 2-10Publisher
ELSEVIER
DOI: 10.1016/j.cattod.2017.05.021
Keywords
Photocatalysis; [4+2] cycloaddition; Ruthenium bipyridine derivatives
Funding
- CONACYT [CB-167446, 600045]
- PAPIIT project [IN226616]
- DGTIC-UNAM [SC16-1-IG-37]
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We report the study of a series of Ru-bipyridine (Ru-Bpy) complexes to correlate their photophysical and electrochemical properties to their performance in [4 + 2] cycloadditions, as a model reaction for electron transfer catalysis. Redox potentials, absorption and emission spectra, quantum yields and DFT calculations are presented to understand the catalytic transformation. The study shows that complex [Ru(Bpy)(3)](PF6)(2) is the more active photocatalyst, giving complete conversion to the product after 2 h reaction under white light. Any substitution in the para position of the Bpy ring decreases the reaction conversion. The [4 + 2] cycloaddition can be performed with different substrates and dienes, using either acetonitrile or nitromethane as solvents. Mechanistic studies suggest that the active catalyst for the transformation is [Ru(Bpy)(3)](3+) and that the rate determining step is the oxidation of [Ru(Bpy)(3)](2+) to generate the corresponding Ru3+ species.
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