Outer-Sphere 2 e^- /2 H⁺ Transfer Reactions of Ruthenium(II)-Amine and Ruthenium(IV)-Amido Complexes.

ABSTRACT: A diverse set of 2 e^- /2 H⁺ reactions are described that interconvert [Ru^II (bpy)(en*)₂ ]²⁺ and [Ru^IV (bpy)(en-H*)₂ ]²⁺ (bpy=2,2'-bipyridine, en*=H₂ NCMe₂ CMe₂ NH₂ , en*-H=H₂ NCMe₂ CMe₂ NH^- ), forming or cleaving different O-H, N-H, S-H, and C-H bonds. The reactions involve quinones, hydrazines, thiols, and 1,3-cyclohexadiene. These proton-coupled electron transfer reactions occur without substrate binding to the ruthenium center, but instead with precursor complex formation by hydrogen bonding. The free energies of the reactions vary over more than 90 kcal mol^-1 , but the rates are more dependent on the t

SUBMITTER: Cattaneo M 

PROVIDER: S-EPMC5812014 | biostudies-literature | 2017 Mar

REPOSITORIES: biostudies-literature