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Photocatalytic function of the B12 complex with the cyclometalated iridium(iii) complex as a photosensitizer under visible light irradiation†
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-12-13 00:00:00 , DOI: 10.1039/c7dt03742b Hui Tian 1, 2, 3, 4, 5 , Hisashi Shimakoshi 1, 2, 3, 4, 5 , Gyurim Park 6, 7, 8, 9 , Sinheui Kim 6, 7, 8, 9 , Youngmin You 6, 7, 8, 9 , Yoshio Hisaeda 1, 2, 3, 4, 5
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-12-13 00:00:00 , DOI: 10.1039/c7dt03742b Hui Tian 1, 2, 3, 4, 5 , Hisashi Shimakoshi 1, 2, 3, 4, 5 , Gyurim Park 6, 7, 8, 9 , Sinheui Kim 6, 7, 8, 9 , Youngmin You 6, 7, 8, 9 , Yoshio Hisaeda 1, 2, 3, 4, 5
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A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(III) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6) as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(II)(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, i.e., the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that the oxidative quenching of the photosensitizer dominated over the reductive quenching pathway.
中文翻译：
B 12配合物与环金属化铱（iii）配合物在可见光照射下的光催化功能†
可见光诱导的三组分催化体系，钴胺素衍生物（B 12）作为催化剂，环金属化铱（III）配合物（Irdfppy，Irppy，Irpbt和[Ir {dF（CF 3）ppy} 2（dtbpy）]]在N 2下开发了作为光敏剂的PF 6）和作为电子源的三乙醇胺。该催化体系显示出比以前使用[Ru（II）（bpy）3 ] Cl 2的催化体系高得多的催化效率。作为用于1,1-双（4-氯苯基）-2,2,2-三氯乙烷（DDT）脱氯反应的光敏剂。值得注意的是，当将Irdfppy用作光敏剂时，获得了基于B 12的显着高营业额数字（超过一万），在报告的研究中排名最高。该光催化系统也成功应用于B 12酶模拟反应，即，是2-溴甲基-2-苯基丙二酸酯的苯基的1，2-迁移。提出了可行的反应机理，该机理涉及DDT脱氯反应过程中激发态光敏剂的初始电子转移，涉及两个猝灭途径，即氧化猝灭途径和还原性猝灭途径。瞬态光致发光实验表明，光敏剂的氧化猝灭在还原猝灭途径中占主导地位。
更新日期：2017-12-13
中文翻译：
B 12配合物与环金属化铱（iii）配合物在可见光照射下的光催化功能†
可见光诱导的三组分催化体系，钴胺素衍生物（B 12）作为催化剂，环金属化铱（III）配合物（Irdfppy，Irppy，Irpbt和[Ir {dF（CF 3）ppy} 2（dtbpy）]]在N 2下开发了作为光敏剂的PF 6）和作为电子源的三乙醇胺。该催化体系显示出比以前使用[Ru（II）（bpy）3 ] Cl 2的催化体系高得多的催化效率。作为用于1,1-双（4-氯苯基）-2,2,2-三氯乙烷（DDT）脱氯反应的光敏剂。值得注意的是，当将Irdfppy用作光敏剂时，获得了基于B 12的显着高营业额数字（超过一万），在报告的研究中排名最高。该光催化系统也成功应用于B 12酶模拟反应，即，是2-溴甲基-2-苯基丙二酸酯的苯基的1，2-迁移。提出了可行的反应机理，该机理涉及DDT脱氯反应过程中激发态光敏剂的初始电子转移，涉及两个猝灭途径，即氧化猝灭途径和还原性猝灭途径。瞬态光致发光实验表明，光敏剂的氧化猝灭在还原猝灭途径中占主导地位。
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