Proton-coupled electron transfer form nitrogen. A N-H/N-D kinetic isotope effect of 41.4

Journal Article · Wed May 12 00:00:00 EDT 1999 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja984325f· OSTI ID:684318

Huynh, M H.V.; Meyer, T J; White, P S ^[1]

---

1. Univ. of North Carolina, Chapel Hill, NC (United States)

An extensive redox chemistry associated with high oxidation state Ru(IV) oxo complexes has been uncovered by kinetic and mechanistic studies. This includes pathways involving well-defined, multiple electron transfer such as O-atom or hydride ion transfer. Large H{sub 2}O/D{sub 2}O solvent kinetic isotope effects have been identified in a series of reactions and interpreted as involving synchronous transfer of an electron and a proton (proton-coupled electron transfer). For example, k(H{sub 2}O)/k(D{sub 2}O) = 30 {+-} 1 for the oxidation of hydroquinone (H{sub 2}O) to benzoquinone (Q) by cis-[Ru{sup IV}(bpy){sub 2}(py)(O)]{sup 2+} at 20.0 {+-} 0.2 C.

• Sponsoring Organization: USDOE, Washington, DC (United States)
• OSTI ID: 684318
• Journal Information: Journal of the American Chemical Society, Vol. 121, Issue 18; Other Information: PBD: 12 May 1999
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
ELECTRON TRANSFER
DEUTERIUM
HEAVY WATER
OXIDATION
QUINONES
BENZOQUINONES
LIGANDS
KINETICS