Understanding the performance of a bisphosphonate Ru water oxidation catalyst

Abstract

Water oxidation catalysts (WOCs) are a key part of generating H2 from water and sunlight, consequently, it is a promising process for the production of clean energy. The mechanism of...

Phenoxylation of Alkynes through Mono‐ and Dual Activation Using Group 11 (Cu, Ag, Au) Catalysts

“…NCI plots computed by the NCIPLOT package, confirmed the significant additional non‐covalent interactions due to the aromatic rings of the IPr* ligand, whereas only the ones between the phenoxide and one of the aryl rings on the diphenylacetylene for the IMe based system (see Figure ). The plot for the IPr ligand is placed in between, and it confirms the effect of the substitution of phenyl by methyl groups, with much less favourable π‐π staking interactions . Thus, NCI plots and EDA analyses here unveil why the sterically more hindered IPr* ligand ends up showing less unfavourable kinetics and thermodynamics than expected for the C–O bond formation.…”

“…The plot for the IPr ligand is placed in between, and it confirms the effect of the substitution of phenyl by methyl groups, with much less favourable π-π staking interactions. [60][61][62][63][64] Thus, NCI plots and EDA analyses here unveil why the sterically more hindered IPr* ligand ends up showing less unfavourable kinetics and thermodynamics than expected for the C-O bond formation.…”

Strategic factors to design the next generation of molecular water oxidation catalysts: Lesson learned from ruthenium complexes

“…[109,110] Concepcion et al [111] and Grotjahn et al [112] in a parallel work presented an innovative idea to replace the carboxylate groups in bda with the phosphates groups to act not only as a ligand to stabilize Ru at a high oxidation state but also as a base near to the catalytic center. [112][113][114] In 2019 a new Ru complex with the general formula [Ru II (H3tPa--N3O)(py)2] + (31) (where H3tPa is deprotonated 2,2':6',2''-terpyridine,6,6''-diphosphonic acid (H4tPa) and pyridine (py)) was prepared which the carboxylate groups was replaced with phosphonate groups and showed high electrocatalytic activity after conversion to a catalyst. In this case, after applying a potential of 1.3 V (vs. NHE) and reaching a high oxidation state (IV), one hydroxide ligand coordinates Ru center, which triggers O-atom insertion into the para position of CH bond of one of the external pyridine groups of equatorial ligand forming the active species (Figure 18, right).…”

Towards Dual-Metal Catalyzed Hydroalkoxylation of Alkynes

“…In the synergistic dual transition metal catalysis [44,45], water oxidation catalysis (WOC) was one of the first cases where two metal-oxo units were required to form the O-O bond at the rate determining step (rds) of the I2M mechanism [46][47][48]. However, competition with water nucleophilic attack (WNA) with the interaction of a metal-oxo unit with an H 2 O molecule to form the O-O bond has never ceased [49], with the potential role of the non-innocent role of the cerium ammonium nitrate (CAN) [50]. Currently, there is controversy not only related to the kinetic requirements, but to the difficulty of colliding two metal units in low catalyst loading conditions.…”