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

Abstract

Formamidinate-bridged Rh2II,II complexes containing diimine ligands of the formula cis-[Rh2II,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 RhIII,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 Rh2II,II/II,I reduction. The Rh2II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh2II,III-hydride. In the case of Rh2-phen2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh2II,II core in the presence of protons to form a Rh2II,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 confirmedmore » H2 formation, and further CH3COOH addition regenerates H2 production, attesting to the robust nature of the architecture. The cis-[Rh2II,II(μ-DTolF)2(NN)2]2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh2II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H+ substrate to H2 fuel.« less

Authors:
 [1];  [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. The Ohio State Univ., Columbus, OH (United States). Dept. of Chemistry and Biochemistry
  2. Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430201
Grant/Contract Number:  
SC0010542; SC0010721
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 20; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; electrocatalysis; dirhodium; formamidinate; diimine ligands; hydrogen

Citation Formats

White, Travis A., Witt, Suzanne E., Li, Zhanyong, Dunbar, Kim R., and Turro, Claudia. New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b01823.
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White, Travis A., Witt, Suzanne E., Li, Zhanyong, Dunbar, Kim R., & Turro, Claudia. New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +. United States. https://doi.org/10.1021/acs.inorgchem.5b01823
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White, Travis A., Witt, Suzanne E., Li, Zhanyong, Dunbar, Kim R., and Turro, Claudia. Fri . "New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +". United States. https://doi.org/10.1021/acs.inorgchem.5b01823. https://www.osti.gov/servlets/purl/1430201.
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@article{osti_1430201,
title = {New Rh 2 (II,II) Architecture for the Catalytic Reduction of H +},
author = {White, Travis A. and Witt, Suzanne E. and Li, Zhanyong and Dunbar, Kim R. and Turro, Claudia},
abstractNote = {Formamidinate-bridged Rh2II,II complexes containing diimine ligands of the formula cis-[Rh2II,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 RhIII,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 Rh2II,II/II,I reduction. The Rh2II,I species is thus protonated at one of the metal centers, resulting in the formation of the corresponding Rh2II,III-hydride. In the case of Rh2-phen2, the reduction of the phen ligand is followed by intramolecular electron transfer to the Rh2II,II core in the presence of protons to form a Rh2II,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-[Rh2II,II(μ-DTolF)2(NN)2]2+ architecture benefits by combining electron-rich formamidinate bridges, a redox-active Rh2II,II core, and electron-accepting NN diimine ligands to allow for the electrocatalysis of H+ substrate to H2 fuel.},
doi = {10.1021/acs.inorgchem.5b01823},
journal = {Inorganic Chemistry},
number = 20,
volume = 54,
place = {United States},
year = {Fri Sep 25 00:00:00 EDT 2015},
month = {Fri Sep 25 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.inorgchem.5b01823
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