title: New Rh2(II,II) Architecture for the Catalytic Reduction of H⁺.
abstract: Formamidinate-bridged Rh2(II,II) complexes containing diimine ligands of the formula cis-[Rh2(II,II)(μ-DTolF)2(NN)2](2+) (Rh2-NN2), where DTolF = p-ditolylformamidinate and NN = dppn (benzo[i]dipyrido[3,2-a:2',3'-h]quinoxaline), dppz (dipyrido[3,2-a:2',3'-c]phenazine), and phen (1,10-phenanthroline), electrocatalytically reduce H(+) to H2 in DMF solutions containing CH3COOH at a glassy carbon electrode. Cathodic scans in the absence of acid display a Rh(III,II/II,II) reduction at -0.90 V vs Fc(+)/Fc followed by NN(0/-) reduction at -1.13, -1.36, and -1.65 V for Rh2-dppn2, Rh2-dppz2, and Rh2-phen2, respectively. Upon the addition of acid, Rh2-dppn2 and Rh2-dppz2 undergo reduction-protonation-reduction at each pyrazine-containing NN ligand prior to the Rh2(II,II/II,I) reduction. The Rh2(II,I) species is then protonated at one of the metal centers, resulting in the formation of the corresponding Rh2(II,III)-hydride. In the case of Rh2-phen2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh2(II,II) core in the presence of protons to form a Rh2(II,III)-hydride species. Further reduction and protonation at the Rh2 core for all three complexes rapidly catalyzes H2 formation with varied calculated turnover frequencies (TOF) and overpotential values (η): 2.6 × 10(4) s(-1) and 0.56 V for Rh2-dppn, 2.8 × 10(4) s(-1) and 0.50 V for Rh2-dppz2, and 5.9 × 10(4) s(-1) and 0.64 V for Rh2-phen2. Bulk electrolysis confirmed H2 formation, and further CH3COOH addition regenerates H2 production, attesting to the robust nature of the architecture. The cis-[Rh2(II,II)(μ-DTolF)2(NN)2](2+) architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh2(II,II) core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H(+) substrate to H2 fuel.
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University , Columbus, Ohio 43210, United States.
authors.forename: Travis A
authors.initials: TA
authors.lastname: White
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University , Columbus, Ohio 43210, United States.
authors.forename: Suzanne E
authors.initials: SE
authors.lastname: Witt
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Zhanyong
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
authors.forename: Kim R
authors.initials: KR
authors.lastname: Dunbar
authors.affiliation: Department of Chemistry and Biochemistry, The Ohio State University , Columbus, Ohio 43210, United States.
authors.forename: Claudia
authors.initials: C
authors.lastname: Turro