Concerted Proton−Electron Transfer in a Ruthenium Terpyridyl-Benzoate System with a Large Separation between the Redox and Basic Sites
作者:Virginia W. Manner、James M. Mayer
DOI:10.1021/ja902942g
日期:2009.7.29
transfer (PCET) reactivity, we have prepared ruthenium complexes with 4'-(4-carboxyphenyl)terpyridine ligands, and studied reactivity with hydrogen atom donors (H-X). Ru(II)(pydic)(tpy-PhCOOH) (Ru(II)PhCOOH), was synthesized in one pot from [(p-cymene)RuCl(2)](2), sodium 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine ([Na(+)]tpy-PhCOO(-)), and disodium pyridine-2,6-dicarboxylate (Na(2)pydic). Ru(II)PhCOOH
为了了解电子和质子接受位点之间的分离如何影响质子耦合电子转移 (PCET) 反应性,我们制备了具有 4'-(4-羧基苯基)三联吡啶配体的钌配合物,并研究了与氢原子供体 (HX) 的反应性)。Ru(II)(pydic)(tpy-PhCOOH) (Ru(II)PhCOOH),由 [(p-cymene)RuCl(2)](2), 4'-(4-carboxyphenyl) 钠在一锅中合成-2,2':6',2''-三联吡啶 ([Na(+)]tpy-PhCOO(-)) 和吡啶-2,6-二羧酸二钠 (Na(2)pydic)。Ru(II)PhCOOH 加 (n)Bu(4)NOH 在 DMF 中产生去质子化的 Ru(II) 络合物,(n)Bu(4)N[Ru(II)(pydic)(tpy-PhCOO)] (Ru( II)PhCOO(-))。Ru(III) 配合物 (Ru(III)PhCOO) 已通过 Ru(II)PhCOO(-)