Aryl–Cl vs heteroatom–Si bond cleavage on the route to the photochemical generation of σ,π-heterodiradicals
作者:Lorenzo Di Terlizzi、Francesca Roncari、Stefano Crespi、Stefano Protti、Maurizio Fagnoni
DOI:10.1007/s43630-021-00119-6
日期:2022.5
The photochemistry of aryl chlorides having a X-SiMe3 group (X = O, NR, S, SiMe2) tethered to the aromatic ring has been investigated in detail, with the aim to generate valuable ϭ,π-heterodiradicals. Two competitive pathways arising from the excited triplet state of the aromatics have been observed, namely heterolysis of the aryl-chlorine bond and homolysis of the X-silicon bond. The former path is
已经详细研究了具有束缚在芳环上的 X-SiMe3 基团 (X = O, NR, S, SiMe2) 的芳基氯化物的光化学,目的是产生有价值的 ϭ,π-杂自由基。已经观察到由芳烃的激发三重态产生的两种竞争途径,即芳基-氯键的异解和X-硅键的均解。前一种途径存在于氯化苯酚和苯胺中,而后者仅适用于甲硅烷基化苯硫酚和芳基硅烷。采用组合的实验/计算方法来解释这种光化学行为。图形摘要。