Department of Chemistry, University of Toronto , 80 St. George Street, Toronto, Ontario M5S 3H6, Canada.
J Am Chem Soc. 2017 Jul 26;139(29):10062-10071. doi: 10.1021/jacs.7b05120. Epub 2017 Jul 17.
Single electron transfer (SET) reactions are effected by the combination of a Lewis acid (e.g., E(CF) E = B or Al) with a small molecule substrate and decamethylferrocene (CpFe). Initially, the corresponding reactions of (PhS) and (PhTe) were shown to give the species [CpFe][PhSB(CF)] 1 and [CpFe][(μ-PhS)(Al(CF))] 2 and [CpFe][(μ-PhTe)(Al(CF))] 3, respectively. Analogous reactions with di-tert-butyl peroxide yielded [CpFe][(μ-HO)(B(CF))] 4 with isobutene while with benzoyl peroxide afforded [CpFe][PhC(O)OE(CF)] (E = B 5, Al 6). Evidence for a radical pathway was provided by the reaction of PhSnH and p-quinone afforded [CpFe][HB(CF)] 7 and [CpFe][(μ-OCH)(E(CF))] (E = B 8, Al 9). In addition, the reaction of TEMPO with Lewis acid and CpFe afforded [CpFe][(CHMeNOE(CF)] (E = B 10, Al 11). Finally, reactions with O, Se, Te and S gave [CpFe][((CF)Al(μ-O)Al(CF))] 12, [CpFe][((CF)Al(μ-Se)Al(CF))] 13, [CpFe][(μ-Te)(Al(CF))] 14 and [CpFe][(μ-S)B(CF))] 15, respectively. The mechanisms of these SET reactions are discussed, and the ramifications are considered.
单电子转移 (SET) 反应是通过路易斯酸（例如 E(CF)，E = B 或 Al）与小分子底物和十甲基二茂铁（CpFe）的组合来实现的。最初，（PhS）和（PhTe）的相应反应显示得到了物种 [CpFe][PhSB(CF)]1 和 [CpFe][(μ-PhS)(Al(CF))]2 和 [CpFe][(μ-PhTe)(Al(CF))]3。用二叔丁基过氧化物进行类似的反应得到了与异丁烯反应的 [CpFe][(μ-HO)(B(CF))]4，而用过氧化苯甲酰得到了 [CpFe][PhC(O)OE(CF)]（E = B5，Al6）。PhSnH 和对苯醌的反应提供了自由基途径的证据，得到了 [CpFe][HB(CF)]7 和 [CpFe][(μ-OCH)(E(CF))]（E = B8，Al9）。此外，TEMPO 与路易斯酸和 CpFe 的反应得到了 [CpFe][(CHMeNOE(CF)]（E = B10，Al11）。最后，与 O、Se、Te 和 S 的反应得到了 [CpFe][((CF)Al(μ-O)Al(CF))]12、[CpFe][((CF)Al(μ-Se)Al(CF))]13、[CpFe][(μ-Te)(Al(CF))]14 和 [CpFe][(μ-S)B(CF))]15。讨论了这些 SET 反应的机制，并考虑了其影响。
