Oxygen−Oxygen Bond Formation by the Ru-Hbpp Water Oxidation Catalyst Occurs Solely via an Intramolecular Reaction Pathway

2009 ◽  
Vol 131 (8) ◽  
pp. 2768-2769 ◽  
Author(s):  
Sophie Romain ◽  
Fernando Bozoglian ◽  
Xavier Sala ◽  
Antoni Llobet
Keyword(s):  
Water Oxidation ◽  
Reaction Pathway ◽  
Bond Formation ◽  
Oxidation Catalyst ◽  
Intramolecular Reaction ◽  
Oxygen Oxygen ◽  
Oxygen Bond

scholarly journals Complete active space analysis of a reaction pathway: Investigation of the oxygen–oxygen bond formation

2020 ◽  
Vol 41 (17) ◽  
pp. 1586-1597 ◽  
Author(s):  
Ruocheng Han ◽  
Sandra Luber
Keyword(s):  
Reaction Pathway ◽  
Bond Formation ◽  
Complete Active Space ◽  
Active Space ◽  
Space Analysis ◽  
Oxygen Oxygen ◽  
Oxygen Bond

ChemInform Abstract: Oxygen-Oxygen Bond Formation Pathways Promoted by Ruthenium Complexes

ChemInform ◽  
2010 ◽  
Vol 41 (20) ◽  
Author(s):  
Sophie Romain ◽  
Laura Vigara ◽  
Antoni Llobet
Keyword(s):  
Bond Formation ◽  
Ruthenium Complexes ◽  
Oxygen Oxygen ◽  
Oxygen Bond

The Mechanism of OO Bond Formation in Tanaka’s Water Oxidation Catalyst

2011 ◽  
Vol 124 (5) ◽  
pp. 1247-1250 ◽  
Author(s):  
Soumya Ghosh ◽  
Mu-Hyun Baik
Keyword(s):  
Water Oxidation ◽  
Bond Formation ◽  
Oxidation Catalyst

scholarly journals From Ru-bda to Ru-bds: a step forward to highly efficient molecular water oxidation electrocatalysts under acidic and neutral conditions

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jing Yang ◽  
Lei Wang ◽  
Shaoqi Zhan ◽  
Haiyuan Zou ◽  
Hong Chen ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Density Functional ◽  
Bond Formation ◽  
Density Functional Theory Calculations ◽  
Oxidation Catalyst ◽  
Nucleophilic Attack ◽  
Molecular Water ◽  
Formation Mechanisms ◽  
Equatorial Position ◽  
Neutral Conditions

AbstractSignificant advances during the past decades in the design and studies of Ru complexes with polypyridine ligands have led to the great development of molecular water oxidation catalysts and understanding on the O−O bond formation mechanisms. Here we report a Ru-based molecular water oxidation catalyst [Ru(bds)(pic)2] (Ru-bds; bds2− = 2,2′-bipyridine-6,6′-disulfonate) containing a tetradentate, dianionic sulfonate ligand at the equatorial position and two 4-picoline ligands at the axial positions. This Ru-bds catalyst electrochemically catalyzes water oxidation with turnover frequencies (TOF) of 160 and 12,900 s−1 under acidic and neutral conditions respectively, showing much better performance than the state-of-art Ru-bda catalyst. Density functional theory calculations reveal that (i) under acidic conditions, the high valent Ru intermediate RuV=O featuring the 7-coordination configuration is involved in the O−O bond formation step; (ii) under neutral conditions, the seven-coordinate RuIV=O triggers the O−O bond formation; (iii) in both cases, the I2M (interaction of two M−O units) pathway is dominant over the WNA (water nucleophilic attack) pathway.

Ligand Geometry Directs OO Bond-Formation Pathway in Ruthenium-Based Water Oxidation Catalyst

2012 ◽  
Vol 124 (24) ◽  
pp. 6069-6072 ◽  
Author(s):  
Somnath Maji ◽  
Laura Vigara ◽  
Francesca Cottone ◽  
Fernando Bozoglian ◽  
Jordi Benet-Buchholz ◽  
...  
Keyword(s):  
Water Oxidation ◽  
Bond Formation ◽  
Oxidation Catalyst ◽  
Formation Pathway

scholarly journals Impact of the Ligand Flexibility and Solvent on the O–O Bond Formation Step in a Highly Active Ruthenium Water Oxidation Catalyst

2018 ◽  
Vol 57 (21) ◽  
pp. 13063-13066 ◽  
Author(s):  
Nitish Govindarajan ◽  
Ambuj Tiwari ◽  
Bernd Ensing ◽  
Evert Jan Meijer
Keyword(s):  
Water Oxidation ◽  
Bond Formation ◽  
Oxidation Catalyst ◽  
Highly Active ◽  
Formation Step

scholarly journals Switching the O-O Bond Formation Pathways of Ru-pda Water Oxidation Catalyst by Third Coordination Sphere Engineering

Research ◽  
2021 ◽  
Vol 2021 ◽  
pp. 1-11
Author(s):  
Yingzheng Li ◽  
Shaoqi Zhan ◽  
Lianpeng Tong ◽  
Wenlong Li ◽  
Yilong Zhao ◽  
...  
Keyword(s):  
Coordination Sphere ◽  
Water Oxidation ◽  
Density Functional ◽  
Electrochemical Polymerization ◽  
Bond Formation ◽  
Kinetic Studies ◽  
Oxidation Catalyst ◽  
Nucleophilic Attack ◽  
Formation Pathway ◽  
Axial Ligands

Water oxidation is a vital anodic reaction for renewable fuel generation via electrochemical- and photoelectrochemical-driven water splitting or CO2 reduction. Ruthenium complexes, such as Ru-bda family, have been shown as highly efficient water-oxidation catalysts (WOCs), particularly when they undergo a bimolecular O-O bond formation pathway. In this study, a novel Ru(pda)-type (pda2– =1,10-phenanthroline-2,9-dicarboxylate) molecular WOC with 4-vinylpyridine axial ligands was immobilized on the glassy carbon electrode surface by electrochemical polymerization. Electrochemical kinetic studies revealed that this homocoupling polymer catalyzes water oxidation through a bimolecular radical coupling pathway, where interaction between two Ru(pda)–oxyl moieties (I2M) forms the O-O bond. The calculated barrier of the I2M pathway by density-functional theory (DFT) is significantly lower than the barrier of a water nucleophilic attack (WNA) pathway. By using this polymerization strategy, the Ru centers are brought closer in the distance, and the O-O bond formation pathway by the Ru (pda) catalyst is switched from WNA in a homogeneous molecular catalytic system to I2M in the polymerized film, providing some deep insights into the importance of third coordination sphere engineering of the water oxidation catalyst.

scholarly journals Intramolecular Oxyl Radical Coupling Promotes O–O Bond Formation in a Homogeneous Mononuclear Mn-based Water Oxidation Catalyst: A Computational Mechanistic Investigation

2017 ◽  
Vol 56 (8) ◽  
pp. 4435-4445 ◽  
Author(s):  
Douglas W. Crandell ◽  
Song Xu ◽  
Jeremy M. Smith ◽  
Mu-Hyun Baik
Keyword(s):  
Water Oxidation ◽  
Bond Formation ◽  
Oxidation Catalyst ◽  
Radical Coupling ◽  
Mechanistic Investigation

scholarly journals Oxygen Atom Transfer as an Alternative Pathway for Oxygen–Oxygen Bond Formation

2020 ◽  
Vol 59 (9) ◽  
pp. 5966-5974 ◽  
Author(s):  
Mehmed Z. Ertem ◽  
Javier J. Concepcion
Keyword(s):  
Oxygen Atom ◽  
Alternative Pathway ◽  
Bond Formation ◽  
Atom Transfer ◽  
Oxygen Atom Transfer ◽  
Oxygen Oxygen ◽  
Oxygen Bond
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