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Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear PtII→GeIV Complex
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-08-16 , DOI: 10.1002/anie.202107485
Mohammadjavad Karimi 1 , Elham S Tabei 1 , Remi Fayad 2 , Mohamed R Saber 1 , Evgeny O Danilov 2 , Cameron Jones 3 , Felix N Castellano 2 , François P Gabbaï 1
Affiliation  

Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph2P)C6H4)2GeIVCl2]PtIICl2 and [(o-(Ph2P)C6H4)2ClGeIII]PtIIICl3, two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph2P)C6H4)2ClGeIII]PtICl with quantum yields of 1.7 % and 3.2 % for the GeIV–PtII and GeIII–PtIII isomers, respectively. Conversion of the GeIV–PtII isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Finally, transient-absorption-spectroscopy studies carried out on the GeIII–PtIII isomer point to a ligand arene–Cl. charge-transfer complex as an intermediate.

中文翻译:

双核 PtII→GeIV 复合物中锗和铂中氯的光驱动消除

为了寻找第 14 族元素的双电子氧化还原行为与其作为光还原消除氯的平台的可能用途之间的联系,我们研究了 [( o -(Ph 2 P)C 6 H 4 ) 2的光化学Ge IV Cl 2 ]Pt II Cl 2和 [( o -(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3,两个新分离的异构复合物。这些研究表明,在氯阱存在的情况下,两种异构体都可以干净地转化为铂锗基复合物 [( o -(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl,量子产率为 1.7% 和Ge IV –Pt II和 Ge III –Pt III异构体分别为 3.2 % 。Ge IV –Pt II 的转换异构体进入铂锗基复合物是光诱导过渡金属/主族元素键形成过程的一个罕见例子。最后,对 Ge III- Pt III异构体进行的瞬态吸收光谱研究指向配体芳烃-Cl 电荷转移复合物作为中间体。
更新日期:2021-09-27
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