New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +

White, Travis A.; Witt, Suzanne E.; Li, Zhanyong; Dunbar, Kim R.; Turro, Claudia

doi:10.1021/acs.inorgchem.5b01823

New Rh ₂ (II,II) Architecture for the Catalytic Reduction of H ⁺

Journal Article · Fri Sep 25 00:00:00 EDT 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b01823· OSTI ID:1430201

White, Travis A. ^[1]; Witt, Suzanne E. ^[2]; Li, Zhanyong ^[3]; Dunbar, Kim R. ^[3]; Turro, Claudia ^[2]

The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry; The Ohio State University
The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry

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 NN⁰/– 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 thus 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 × 10⁴ s^–1 and 0.56 V for Rh₂-dppn, 2.8 × 10⁴ s^–1 and 0.50 V for Rh₂-dppz₂, and 5.9 × 10⁴ 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.

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0010542; SC0010721

OSTI ID:: 1430201

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 20 Vol. 54; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

14 SOLAR ENERGY
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
diimine ligands
dirhodium
electrocatalysis
formamidinate
hydrogen