Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Peng, Li; Liu, Jing‐Lin; Han, Sheng; Deng, Wei; Yao, Zhonghua

doi:10.1002/aoc.5040

Cited by 12 publications

(4 citation statements)

References 85 publications

(84 reference statements)

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“…Imine donor ligands are rarely utilized in water oxidation catalysts, with the exception of cobalt and manganese Schiff base complexes and several binuclear iridium and ruthenium systems. [80][81][82][83][84] Cyclam ligands with methylated bridging propane moieties produce a less active catalyst (both in terms of TOF and TON), as becomes clear by comparing complexes and 3. The methylation of nitrogen donor atoms also has a negative effect on the activity, as complex 4 is less active than 2, and 5 does not show any activity.…”

Section: Resultsmentioning

confidence: 95%

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes

Hessels

Masferrer‐Rius

et al. 2020

ChemSusChem

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The development of novel water oxidation catalysts is important in the context of renewable fuels production. Ligand design is one of the key tools to improve the activity and stability of molecular catalysts. The establishment of ligand design rules can facilitate the development of improved molecular catalysts. In this paper it is shown that chemical oxidants can be used to probe oxygen evolution activity for nickel‐based systems, and trends are reported that can improve future ligand design. Interestingly, different ligand effects were observed in comparison to other first‐row transition metal complexes. For example, nickel complexes with secondary amine donors were more active than with tertiary amine donors, which is the opposite for iron complexes. The incorporation of imine donor groups in a cyclam ligand resulted in the fastest and most durable nickel catalyst of our series, achieving oxygen evolution turnover numbers up to 380 and turnover frequencies up to 68 min−1 in a pH 5.0 acetate buffer using Oxone as oxidant. Initial kinetic experiments with this catalyst revealed a first order in chemical oxidant and a half order in catalyst. This implies a rate‐determining oxidation step from a dimeric species that needs to break up to generate the active catalyst. These findings lay the foundation for the rational design of molecular nickel catalysts for water oxidation and highlight that catalyst design rules are not generally applicable for different metals.

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Section: Resultsmentioning

confidence: 95%

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes

Hessels

Masferrer‐Rius

et al. 2020

ChemSusChem

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“…Single crystals of the individual enantiomers 2 were selected using the microscope with the polarized lighting (Figure S6). Each isomer from the enantiomeric pair (S-2 and R-2) was structurally characterized independently with Flack parameters −0.028 (15) and −0.015 (9), respectively, which are very close to zero within the standard uncertainty, indicative of the correct absolute structure determination (Figure 4). The asymmetric unit in S-2 and R-2 contains one molecule.…”

Section: Crystal Structures Of the Coordination Compoundsmentioning

confidence: 98%

“…Recently, iridium(III) and rhodium(III) complexes have gained a lot of attention as luminescent agents [1][2][3][4], chemo-and biosensors [5][6][7][8], biologically active compounds [9][10][11][12], and especially as catalysts [13][14][15]. Chiral half-sandwich Cp*Ir and Cp*Rh complexes were successfully applied in asymmetric catalysis, most importantly, the catalytic activation of C-H bonds [16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Iridium(III) and Rhodium(III) Half-Sandwich Coordination Compounds with 11H-Indeno[1,2-b]quinoxalin-11-one Oxime: A Case of Spontaneous Resolution of Rh(III) Complex

2022

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Two half-sandwich iridium(III) and rhodium(III) complexes with 11H-indeno[1,2-b]quinoxalin-11-one oxime (IQ-1) ligand were prepared by the reaction of the proligand with [M(Cp*)Cl2]2 (M = Ir, Rh) dimers. The reaction between IQ-1 and [Ir(Cp*)Cl2]2 in methanol gave the complex [Ir(Cp*)(IQ-1)Cl] (1), which crystallized in a centrosymmetric space group as a true racemate. Whereas complex [Rh(Cp*)(IQ-1)Cl] (2) in the form of a racemic conglomerate was obtained by the reaction of [Rh(Cp*)Cl2]2 and IQ-1 in methanol. The crystal structures of complexes 1 and 2 (R and S enantiomers) were determined by X-ray diffraction analysis, and the structural features were compared in order to understand the structural factors leading to the spontaneous enantiomer resolution of the rhodium(III) complex. In the crystal packing of 1, intermolecular C–H···C contacts between a pair of enantiomers link the molecules into centrosymmetric dimers and lead to the formation of heterochiral crystals of 1. In contrast, the intramolecular contacts CH···Cl and CH···C in complex 2 bind all three ligands around the chiral Rh(III) metal center. In addition, a combination of intermolecular CH···O and CH···C contacts leads to the formation of a homochiral supramolecular structure. These interactions altogether reinforce the spontaneous resolution in complex 2.

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“…Table S5. Comparison of different parameters of complexes for water oxidation in recent years [ 69 , 70 , 71 , 72 ]. Table S6.…”

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confidence: 99%

Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation

Zhao

Jian

et al. 2023

Molecules

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One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear complex [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L = N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that the Mn(III) ion in 1 has an octahedral coordination structure, whereas the Mn(II) ion in 2 possesses a trigonal bipyramidal configuration and the Cu(II) ion in 2 is four-coordinated with a square-planar geometry. Electrochimerical catalytic investigation demonstrates that the two complexes can electrochemically catalyze water oxidation and CO2 reduction simultaneously. The coordination environments of the Mn(III), Mn(II), and Cu(II) ions in 1 and 2 were provided by the Schiff base ligand (L) and labile solvent molecules. The coordinately unsaturated environment of the Cu(II) center in 2 can perfectly facilitate the catalytic performance of 2. Complexes 1 and 2 display that the over potentials for water oxidation are 728 mV and 216 mV, faradaic efficiencies (FEs) are 88% and 92%, respectively, as well as the turnover frequency (TOF) values for the catalytic reduction of CO2 to CO are 0.38 s−1 at −1.65 V and 15.97 s−1 at −1.60 V, respectively. Complex 2 shows much better catalytic performance for both water oxidation and CO2 reduction than that of complex 1, which could be owing to a structural reason which is attributed to the synergistic catalytic action of the neighboring Mn(III) and Cu(II) active sites in 2. Complexes 1 and 2 are the first two compounds coordinated with Schiff base ligand for both water oxidation and CO2 reduction. The finding in this work can offer significant inspiration for the future development of electrocatalysis in this area.

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Half‐sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double‐site

Cited by 12 publications

References 85 publications

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes

Nickel is a Different Pickle: Trends in Water Oxidation Catalysis for Molecular Nickel Complexes

Iridium(III) and Rhodium(III) Half-Sandwich Coordination Compounds with 11H-Indeno[1,2-b]quinoxalin-11-one Oxime: A Case of Spontaneous Resolution of Rh(III) Complex

Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation

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