We report three binuclear species [LCoIII2(μ-Pz)2](ClO4)3 (1), [LNiII2(CH3OH)2Cl2]ClO4 (2), and [LZnII2Cl2]PF6 (3) supported by the deprotonated form of the ligand 2,6-bis[bis(2-pyridylmethyl) amino-methyl]-4-methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species 1–3 had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species 1 and 2 reduced H2O to H2 effectively at an applied potential of -1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species 3 lacked activity and was used as a negative control to eliminate the possibility of ligand-based catalysis. Pre- and post-catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species 1 showed structural, rather than electronic cooperativity, while species 2 displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.
Morgan, Fredricka, et al. "Distinct Bimetallic Cooperativity Among Water Reduction Catalysts Containing [Co<sup>III</sup>Co<sup>III</sup>], [Ni<sup>II</sup>Ni<sup>II</sup>], and [Zn<sup>II</sup>Zn<sup>II</sup>] Cores." Chemistry - A European Journal, vol. 28, no. 23, Feb. 2022. https://doi.org/10.1002/chem.202104426
Morgan, Fredricka, Schaugaard, Richard, Anderson, Dennis, Schlegel, H. Bernhard, & Verani, Cláudio N. (2022). Distinct Bimetallic Cooperativity Among Water Reduction Catalysts Containing [Co<sup>III</sup>Co<sup>III</sup>], [Ni<sup>II</sup>Ni<sup>II</sup>], and [Zn<sup>II</sup>Zn<sup>II</sup>] Cores. Chemistry - A European Journal, 28(23). https://doi.org/10.1002/chem.202104426
@article{osti_1976300,
author = {Morgan, Fredricka and Schaugaard, Richard and Anderson, Dennis and Schlegel, H. Bernhard and Verani, Cláudio N.},
title = {Distinct Bimetallic Cooperativity Among Water Reduction Catalysts Containing [Co<sup>III</sup>Co<sup>III</sup>], [Ni<sup>II</sup>Ni<sup>II</sup>], and [Zn<sup>II</sup>Zn<sup>II</sup>] Cores},
annote = {We report three binuclear species [LCoIII2(μ-Pz)2](ClO4)3 (1), [LNiII2(CH3OH)2Cl2]ClO4 (2), and [LZnII2Cl2]PF6 (3) supported by the deprotonated form of the ligand 2,6-bis[bis(2-pyridylmethyl) amino-methyl]-4-methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species 1–3 had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species 1 and 2 reduced H2O to H2 effectively at an applied potential of -1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species 3 lacked activity and was used as a negative control to eliminate the possibility of ligand-based catalysis. Pre- and post-catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species 1 showed structural, rather than electronic cooperativity, while species 2 displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.},
doi = {10.1002/chem.202104426},
url = {https://www.osti.gov/biblio/1976300},
journal = {Chemistry - A European Journal},
issn = {ISSN 0947-6539},
number = {23},
volume = {28},
place = {United States},
publisher = {Wiley},
year = {2022},
month = {02}}
