Concerted proton-electron transfer in a ruthenium terpyridyl-benzoate system with a large separation between the redox and basic sites.

ABSTRACT: To understand how the separation between the electron and proton-accepting sites affects proton-coupled electron 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 plus (n)Bu(4)NOH in DMF yields the deprotonated Ru(II) complex, (n)Bu(4)N[Ru(II)(pydic)(tpy-PhCOO)] (Ru(II)PhCOO(-)). The Ru(III) complex (Ru(III)PhCOO) has been isolated by one-electron oxidation of Ru(II)PhCOO(-) with triarylaminium radical cations (NAr(3)(*+)). The bond dissoc

SUBMITTER: Manner VW 

PROVIDER: S-EPMC2765064 | biostudies-literature | 2009 Jul

REPOSITORIES: biostudies-literature