通过单电子转移至给体-受体加合物形成含锌自由基阴离子
Zinc-Containing Radical Anions via Single Electron Transfer to Donor-Acceptor Adducts.
作者信息
Cao Levy L, Bamford Karlee L, Liu Liu Leo, Stephan Douglas W
机构信息
Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.
出版信息
Chemistry. 2018 Mar 15;24(16):3980-3983. doi: 10.1002/chem.201800607. Epub 2018 Feb 27.
Reactions of [Cp* Fe] with the Lewis acid [Zn(C F ) ] in the presence of [(PhC(S)S) ], 9,10-phenanthrenedione or 4,5-pyrenedione yield the salt [Cp* Fe][(PhC(S)S)Zn(C F ) ] 1, [Cp* Fe][((C H O )Zn(C F ) )⋅] 4, and [Cp* Fe][((C H O )Zn(C F ) )⋅] 5, respectively. The latter two species represent the first examples of isolable zinc-containing radical anions. While [(PhC(S)S) ] binds weakly to [Zn(C F ) ], the diones afford the isolable adducts [(C H O )Zn(C F ) ] 2 and [(C H O )Zn(C F ) ] 3. Cyclic voltammetry and computational studies support the view that 4 and 5 are formed via single electron transfer (SET) to the donor-acceptor adducts, 2 and 3, respectively. Subsequent treatment of 4 and 5 with [NC H NMe ] affords [Zn(C F ) (NC H NMe ) ] with liberation of the dione, and regeneration of [Cp* Fe].
在[(PhC(S)S)]、9,10-菲醌或4,5-芘醌存在的情况下，[CpFe]与路易斯酸[Zn(CF)]反应，分别生成盐[CpFe][(PhC(S)S)Zn(CF)] 1、[CpFe][((CHO)Zn(CF))·] 4和[CpFe][((CHO)Zn(CF))·] 5。后两种物质是可分离的含锌自由基阴离子的首例。虽然[(PhC(S)S)]与[Zn(CF)]的结合较弱，但醌类可生成可分离的加合物[(CHO)Zn(CF)] 2和[(CHO)Zn(CF)] 3。循环伏安法和计算研究支持这样的观点，即4和5分别通过向供体-受体加合物2和3进行单电子转移(SET)形成。用[NC H NMe]对4和5进行后续处理，可得到[Zn(CF)(NC H NMe)]，同时醌类被释放出来，[Cp*Fe]得以再生。
Zotero 插件