Structure–Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands

Muller, Keven; Sun, Yu; Heimermann, Andreas; Menges, Fabian; Niedner‐Schatteburg, Gereon; Wüllen, Christoph van; Thiel, Werner R.

doi:10.1002/chem.201204199

Cited by 34 publications

(20 citation statements)

References 69 publications

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“…Figure presents one example that contains a bicyclic pyridinylazolato ligand together with two phospine ligands and one hydrogen atom. Derivatives of this complex in which a hydrogen atom at the pyridinyl moiety is substituted by a methyl or phosphine group were studied with respect to their catalytic activity for carbon dioxide hydrogenation . For establishing an automated, shell‐wise ligand construction algorithm with GdMC as a scoring principle, we will design this CO 2 ‐binding complex from scratch.…”

Section: The Design Target: Co2 Activationmentioning

confidence: 99%

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Stabilization of activated fragments by shell‐wise construction of an embedding environment

2017

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An activated fragment which is structurally unstable when considered isolated can be stabilized through binding to a suitable molecular environment; for instance, to a transition-metal fragment. The metal fragment may be designed in a shell-wise build-up of a surrounding molecular environment. However, adding more and more atoms in a consecutive fashion soon leads to a combinatorial explosion of structures, which is unfeasible to handle without automation. Here, we present a fully automated and parallelized framework that constructs such an embedding environment atom-wise. Molecular realizations of such an environment are constructed based on simple heuristic rules intended to screen a sufficiently large portion of the possible compound space and are then subsequently optimized by electronic structure methods. (Constrained-optimized) structures are then evaluated with respect to a scoring function, for which we choose here the concept of gradient-driven molecule construction. This concept searches for structure modifications that reduce the forces on all atoms. We develop and analyze our approach at the example of CO activation by reproducing a known compound and mapping out possible alternative structures and their effect on the stabilization of a (bent) CO ligand. For all generated structures, the nuclear gradient on the activated fragment and its coordination energy are evaluated to steer the design process. © 2017 Wiley Periodicals, Inc.

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Section: The Design Target: Co2 Activationmentioning

confidence: 99%

“… Left : the BP86/def2‐TZVP optimized structure of the Ru(II) complex with a large bidentate pyridinylazolato ligand synthesized by Muller et al Right : its Lewis structure. [Color figure can be viewed at http://wileyonlinelibrary.com]…”

Section: The Design Target: Co2 Activationmentioning

confidence: 99%

Stabilization of activated fragments by shell‐wise construction of an embedding environment

2017

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“…15,16 Recently, the structure-reactivity relationship of a pyridinylazolate ligand using a ruthenium-based complex has been investigated by Thiel. 17 Very recently, Laurenczy reported the base-free production of highly concentrated formic acid (> 1.9 M) catalyzed by a ruthenium PTA complex (PTA: 1,3,5-triaza-7-phosphaadamantane) in DMSO at 10 MPa. 18 The direct production of formic acid without any additive is very attractive from the viewpoint of hydrogen storage.…”

Section: Introductionmentioning

confidence: 99%

CO₂ Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand

et al. 2015

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The catalytic cycle for the production of formic acid by CO2 hydrogenation and the reverse reaction have received renewed attention because they are viewed as offering a viable scheme for hydrogen storage and release. In this Forum Article, CO2 hydrogenation catalyzed by iridium complexes bearing sophisticated N^N-bidentate ligands is reported. We describe how a ligand containing hydroxy groups as proton-responsive substituents enhances the catalytic performance by an electronic effect of the oxyanions and a pendent-base effect through secondary coordination sphere interactions. In particular, [(Cp*IrCl)2(TH2BPM)]Cl2 (Cp* = pentamethylcyclopentadienyl; TH2BPM = 4,4',6,6'-tetrahydroxy-2,2'-bipyrimidine) enormously promotes the catalytic hydrogenation of CO2 in basic water by these synergistic effects under atmospheric pressure and at room temperature. Additionally, newly designed complexes with azole-type ligands were applied to CO2 hydrogenation. The catalytic efficiencies of the azole-type complexes were much higher than that of the unsubstituted bipyridine complex [Cp*Ir(bpy)(OH2)]SO4. Furthermore, the introduction of one or more hydroxy groups into ligands such as 2-pyrazolyl-6-hydroxypyridine, 2-pyrazolyl-4,6-dihydroxypyrimidine, and 4-pyrazolyl-2,6-dihydroxypyrimidine enhanced the catalytic activity. It is clear that the incorporation of additional electron-donating functionalities into proton-responsive azole-type ligands is effective for promoting further enhanced hydrogenation of CO2.

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“…Compounds H4L 1 and H5L 2 were obtained by acylation of triazolylcarboxylic acid hydrazides by picolinic acid iminoester, with subsequent cyclization providing title compounds (Scheme 1), which is a common method for the preparation of 1,2,4-triazoles [11,12]. The first step of the reaction proceeds is coordinated in the anionic form [13,14]. The obtained complexes, especially [(UO2)(H3L 2 )](СH3OH), so are poorly soluble in DMSO or other solvents, and therefore we were unable to obtain a suitable for analysis 13 C NMR spectrum for [(UO2)(H2L 1)](СH3OH)…”

Section: Resultsmentioning

confidence: 99%

Synthesis of 3-(2-Hydroxyphenyl)-5-(2-Pyridinyl)-1,2,4-triazoles as a potential chelate ligand for Uranyl ion

et al. 2020

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Two new uranyl complexes with the molecular formula [(UO2)(H2L1)](СH3OH) and [(UO2)(H3L2)](СH3OH) {H4L1 = 2-[5-[[5-[[5-(2-pyridyl)-1H-1,2,4-triazol-3‑yl]methyl]-1H-1,2,4-triazol-3-yl]methyl]-1H-1,2,4-triazol-3-yl]phenol and H5L2 = 2-[5-[[5-[[5-[[5-(2-pyridyl)-1H-1,2,4‑triazol-3-yl]methyl]-1H-1,2,4-triazol-3-yl]methyl]-1H-1,2,4-triazol-3-yl]methyl]-1H-1,2,4-triazol-3-yl]phenol)} have been synthesized. All compounds have been characterized by NMR and IR spectroscopy. With H4L1 and H5L2 uranyl ion forms mononuclear complexes. In [(UO2)(H3L2)](СH3OH) pyridyl nitrogen was uncoordinated and bonding of H5L2 was realized only through phenol oxygen and N4-nitrogens of triazole cycles.

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Structure–Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands

Cited by 34 publications

References 69 publications

Stabilization of activated fragments by shell‐wise construction of an embedding environment

Stabilization of activated fragments by shell‐wise construction of an embedding environment

CO₂ Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand

Synthesis of 3-(2-Hydroxyphenyl)-5-(2-Pyridinyl)-1,2,4-triazoles as a potential chelate ligand for Uranyl ion

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Structure–Reactivity Relationships in the Hydrogenation of Carbon Dioxide with Ruthenium Complexes Bearing Pyridinylazolato Ligands

Cited by 34 publications

References 69 publications

Stabilization of activated fragments by shell‐wise construction of an embedding environment

Stabilization of activated fragments by shell‐wise construction of an embedding environment

CO2 Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand

Synthesis of 3-(2-Hydroxyphenyl)-5-(2-Pyridinyl)-1,2,4-triazoles as a potential chelate ligand for Uranyl ion

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CO₂ Hydrogenation Catalyzed by Iridium Complexes with a Proton-Responsive Ligand