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Singlet Oxygen Generation, Quenching and Reactivity with Metal Thiolates†
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-07-09 , DOI: 10.1111/php.13487 Charlotte G Monsour 1 , Cassandra M Decosto 1 , Bliss J Tafolla-Aguirre 1 , Luis A Morales 1 , Matthias Selke 1
Photochemistry and Photobiology ( IF 2.6 ) Pub Date : 2021-07-09 , DOI: 10.1111/php.13487 Charlotte G Monsour 1 , Cassandra M Decosto 1 , Bliss J Tafolla-Aguirre 1 , Luis A Morales 1 , Matthias Selke 1
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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.
中文翻译：
单线态氧的产生、淬灭和与金属硫醇盐的反应†
金属硫醇盐络合物可以作为光敏剂产生单线态氧、单线态氧猝灭剂，并且它们可以与单线态氧发生化学反应，导致氧化的硫醇盐配体。这篇综述涵盖了硫醇配体与单线态氧的所有化学反应（到 2021 年初）。由于其中一些反应是自敏化光氧化反应，因此还讨论了金属配合物产生单线态氧。介绍了质子与非质子条件的影响等机理特征，并与比较容易理解的有机硫化物光氧化进行了比较。通常，单线态氧去除的总速率与硫醇盐配体的亲核性相关，而硫醇盐配体的亲核性又会受到金属的影响。本次调查发现了一些有趣的反应模式： 带有芳基硫醇盐配体的金属硫醇盐络合物在与单线态氧反应时似乎只产生亚磺酸盐（金属结合的砜）产物。相反，带有烷基硫醇盐配体的金属硫醇盐络合物可产生亚磺酸盐和/或亚磺酸盐（金属结合的亚砜）产物。已经为这些反应提出了几种机制途径，但目前尚不清楚任何中间体的确切性质。
更新日期：2021-07-09
中文翻译：
单线态氧的产生、淬灭和与金属硫醇盐的反应†
金属硫醇盐络合物可以作为光敏剂产生单线态氧、单线态氧猝灭剂，并且它们可以与单线态氧发生化学反应，导致氧化的硫醇盐配体。这篇综述涵盖了硫醇配体与单线态氧的所有化学反应（到 2021 年初）。由于其中一些反应是自敏化光氧化反应，因此还讨论了金属配合物产生单线态氧。介绍了质子与非质子条件的影响等机理特征，并与比较容易理解的有机硫化物光氧化进行了比较。通常，单线态氧去除的总速率与硫醇盐配体的亲核性相关，而硫醇盐配体的亲核性又会受到金属的影响。本次调查发现了一些有趣的反应模式： 带有芳基硫醇盐配体的金属硫醇盐络合物在与单线态氧反应时似乎只产生亚磺酸盐（金属结合的砜）产物。相反，带有烷基硫醇盐配体的金属硫醇盐络合物可产生亚磺酸盐和/或亚磺酸盐（金属结合的亚砜）产物。已经为这些反应提出了几种机制途径，但目前尚不清楚任何中间体的确切性质。
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