Concerted Proton−Electron Transfer in a Ruthenium Terpyridyl-Benzoate System with a Large Separation between the Redox and Basic Sites

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 dissociation free energy (BDFE) of the O-H bond in Ru(II)PhCOOH is calculated from pK(a) and E(1/2) measurements as 87 kcal mol(-1), making Ru(III)PhCOO a strong hydrogen atom acceptor. There are 10 bonds and ca. 11.2 A separating the metal from the carboxylate basic site in Ru(III)PhCOO. Even with this separation, Ru(III)PhCOO oxidizes the hydrogen atom donor TEMPOH (BDFE = 66.5 kcal mol(-1), DeltaG(o)(rxn) = -21 kcal mol(-1)) by removal of an electron and a proton to form Ru(II)PhCOOH and TEMPO radical in a concerted proton-electron transfer (CPET) process. The second order rate constant for this reaction is (1.1 +/- 0.1) x 10(5) M(-1) s(-1) with k(H)/k(D) = 2.1 +/- 0.2, similar to the observed kinetics in an analogous system without the phenyl spacer, Ru(III)(pydic)(tpy-COO(-)) (Ru(III)COO). In contrast, hydrogen transfer from 2,6-di-tert-butyl-p-methoxyphenol [(t)Bu(2)(OMe)ArOH] to Ru(III)PhCOO is several orders of magnitude slower than the analogous reaction with Ru(III)COO.