Journal
PHOTOCHEMISTRY AND PHOTOBIOLOGY
Volume 97, Issue 6, Pages 1219-1240Publisher
WILEY
DOI: 10.1111/php.13487
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Funding
- NSF-CREST program [HRD-1547723]
- NIH-NIGMS MARC program [T34 GM08228]
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Metal thiolate complexes can undergo various chemical reactions with singlet oxygen, leading to different oxidized thiolate ligands. The reactivity is influenced by the nucleophilicity of the thiolate ligand and the type of metal present.
Metal thiolate complexes can act as photosensitizers for the generation of singlet oxygen, quenchers of singlet oxygen, and they may undergo chemical reactions with singlet oxygen leading to oxidized thiolate ligands. This review covers all of the chemical reactions of thiolate ligands with singlet oxygen (through early 2021). Since some of these reactions are self-sensitized photooxidations, singlet oxygen generation by metal complexes is also discussed. Mechanistic features such as the effects of protic vs. aprotic conditions are presented and compared with the comparatively well-understood photooxidation of organic sulfides. In general, the total rate of singlet oxygen removal correlates with the nucleophilicity of the thiolate ligand which in turn can be influenced by the metal. Some interesting patterns of reactivity have been noted as a result of this survey: Metal thiolate complexes bearing arylthiolate ligands appear to exclusively produce sulfinate (metal-bound sulfone) products upon reaction with singlet oxygen. In contrast, metal thiolate complexes bearing alkylthiolate ligands may produce sulfinate and/or sulfenate (metal-bound sulfoxide) products. Several mechanistic pathways have been proposed for these reactions, but the exact nature of any intermediates remains unknown at this time.
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