Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Rhoda-Electrocatalyzed Bimetallic C-H Oxygenation by Weak O-Coordination.

ABSTRACT: Rhodium-electrocatalyzed arene C-H oxygenation by weakly O-coordinating amides and ketones have been established by bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed by the judicious choice of current, enabling twofold C-H functionalization. Detailed mechanistic studies by experiment, mass spectroscopy and cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced C-H activation by a bimetallic rhodium catalysis manifold.

SUBMITTER: Tan X

PROVIDER: S-EPMC8252749 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Rhoda-Electrocatalyzed Bimetallic C-H Oxygenation by Weak O-Coordination.

Tan Xuefeng X Massignan Leonardo L Hou Xiaoyan X Frey Johanna J Oliveira João C A JCA Hussain Masoom Nasiha MN Ackermann Lutz L

Angewandte Chemie (International ed. in English) 20210507 24

Rhodium-electrocatalyzed arene C-H oxygenation by weakly O-coordinating amides and ketones have been established by bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed by the judicious choice of current, enabling twofold C-H functionalization. Detailed mechanistic studies by experiment, mass spectroscopy and cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced C-H activation by a bimetallic rhodium catalysis manifold. ...[more]

PMID: 33651910

Similar Datasets

Rhoda-Electrocatalyzed C-H Methylation and Paired Electrocatalyzed C-H Ethylation and Propylation.

Project description:The use of electricity over traditional stoichiometric oxidants is a promising strategy for sustainable molecular assembly. Herein, we describe the rhoda-electrocatalyzed C-H activation/alkylation of several N-heteroarenes. This catalytic approach has been successfully applied to several arenes, including biologically relevant purines, diazepam, and amino acids. The versatile C-H alkylation featured water as a co-solvent and user-friendly trifluoroborates as alkylating agents. Finally, the rhoda-electrocatalysis with unsaturated organotrifluoroborates proceeded by paired electrolysis.

| S-EPMC9299020 | biostudies-literature

Electrochemical Access to Aza-Polycyclic Aromatic Hydrocarbons: Rhoda-Electrocatalyzed Domino Alkyne Annulations.

Project description:Nitrogen-doped polycyclic aromatic hydrocarbons (aza-PAHs) have found broad applications in material sciences. Herein, a modular electrochemical synthesis of aza-PAHs was developed via a rhodium-catalyzed cascade C-H activation and alkyne annulation. A multifunctional O-methylamidoxime enabled the high chemo- and regioselectivity. The isolation of two key rhodacyclic intermediates made it possible to delineate the exact order of three C-H activation steps. In addition, the metalla-electrocatalyzed multiple C-H transformation is characterized by unique functional group tolerance, including highly reactive iodo and azido groups.

| S-EPMC7155118 | biostudies-literature

Insights into Ruthenium(II/IV)-Catalyzed Distal C-H Oxygenation by Weak Coordination.

Project description:C-H hydroxylation of aryl acetamides and alkyl phenylacetyl esters was accomplished via challenging distal weak O-coordination by versatile ruthenium(II/IV) catalysis. The ruthenium(II)-catalyzed C-H oxygenation of aryl acetamides proceeded through C-H activation, ruthenium(II/IV) oxidation and reductive elimination, thus providing step-economical access to valuable phenols. The p-cymene-ruthenium(II/IV) manifold was established by detailed experimental and DFT-computational studies.

| S-EPMC7756554 | biostudies-literature

Rhoda Rebecca Law

Project description: Not available

| S-EPMC416650 | biostudies-literature

Giant Enhancement of Carrier Mobility in Bimetallic Coordination Polymers.

Project description:Electrically conductive metal-organic coordination polymers (CPs) are promising candidates for a variety of technological applications. However, poor energetic and spatial overlap between the sp-electrons of organic ligands and the d-electrons of metal ion often blocks an effective charge transport (mobility) across CPs. Herein, we present a bimetallic design principle for enhancing carrier mobility in CPs. Bimetallic CPs of Fe(III) and Cr(III) ions coordinated to 1,3,5-benzenetricarboxylic acid (BTC) ligand (Fe-BTC-Cr) exhibited remarkably high carrier mobility at the matching mole ratio (1:1) with enhancement factors of 102 and 104 in comparison to those of monometallic parents, Fe-BTC and Cr-BTC, respectively. The observation was substantiated by lowering of the band gap between the valence band and the conduction band upon the formation of a hybrid p-n-type structure in the bimetallic CPs. The direct current conductivity values of the CPs measured by four-probe technique were in good agreement with the alternating current conductivity values obtained from the electrochemical impedance spectroscopy. Our flexible approach of picking and choosing the appropriate combination of metal ions from the periodic table is expected to generate various CPs with desirable semiconducting properties.

| S-EPMC6641710 | biostudies-literature

Oxygenation of cobalt porphyrinates: coordination or oxidation?

Project description:The X-ray characterization of the five-coordinate picket-fence porphyrin complex, [Co(TpivPP)(2-MeHIm)], is reported. The complex has the displacement of cobalt from the porphyrin plane = 0.15 A, and Co-N(Im) = 2.145(3) and (Co-N(p))(av) = 1.979(3) A. This five-coordinate complex, in the presence of dioxygen and excess 2-methylimidazole, undergoes an unanticipated, photoinitiated atropisomerization of the porphyrin ligand, oxidation of cobalt(II), and the formation of the neutral cobalt(III) complex [Co(alpha,alpha,beta,beta-TpivPP)(2-MeHIm)(2-MeIm(-)]. Two distinct examples of this complex have been structurally characterized, and both have structural parameters consistent with cobalt(III). The two new Co(III) porphyrin complexes have axial Co-N(Im) distances ranging from 1.952 to 1.972 A, but which allow for the distinction between imidazole and imidazolate. An interesting intermolecular hydrogen bonding network is observed that leads to infinite helical chains. UV-vis spectroscopic study suggests that [Co(TpivPP)(2-MeHIm)(O(2))] is an intermediate state for the oxidation reaction and that the atropisomerization process is photocatalyzed. A reaction route is proposed based on the spectroscopic studies.

| S-EPMC2826529 | biostudies-literature

Phenylpyridyl-Fused Boroles: A Unique Coordination Mode and Weak B-N Coordination-Induced Dual Fluorescence.

Project description:Using 4-phenylpyridine or 2-phenylpyridine in place of biphenyl, two electron-poor phenylpyridyl-fused boroles, [TipPBB1]4 and TipPBB2 were prepared. [TipPBB1]4 adopts a unique coordination mode and forms a tetramer with a cavity in both the solid state and solution. The boron center of TipPBB2 is 4-coordinate in the solid state but the system dissociates in solution, leading to 3-coordinate borole species. Compared to its borafluorene analogues, the electron-accepting ability of TipPBB2 is largely enhanced by the pyridyl group. TipPBB2 exhibits dual fluorescence in solution due to an equilibrium between free TipPBB2 and a weak intermolecular coordination adduct with a second molecule. This equilibrium was further investigated by low-temperature NMR spectroscopy and photophysical studies. Theoretical studies indicate that the highest occupied molecular orbital (HOMO) of TipPBB2 localizes at the Tip group, in contrast to its borafluorene derivatives, wherein the HOMOs are localized on the borafluorene cores.

| S-EPMC7986225 | biostudies-literature

Changes in ligand coordination mode induce bimetallic C-C coupling pathways.

Project description:Carbon-carbon coupling is one of the most powerful tools in the organic synthesis arsenal. Known methodologies primarily exploit monometallic Pd0/PdII catalytic mechanisms to give new C-C bonds. Bimetallic C-C coupling mechanisms that involve a PdI/PdII redox cycle, remain underexplored. Thus, a detailed mechnaistic understanding is imperative for the development of new bimetallic catalysts. Previously, a PdII-Me dimer (1) supported by L1, which has phosphine and 1-azaallyl donor groups, underwent reductive elimination to give ethane, a PdI dimer, a PdII monometallic complex, and Pd black. Herein, a comprehensive experimental and computational study of the reactivity of 1 is presented, which reveals that the versatile coordination chemistry of L1 promotes bimetallic C-C bond formation. The phosphine 1-azaallyl ligand adopts various bridging modes to maintain the bimetallic structure throughout the C-C bond forming mechanism, which involves intramolecular methyl transfer and 1,1-reductive elimination from one of the palladium atoms. The minor byproduct, methane, likely forms through a monometallic intermediate that is sensitive to solvent C-H activation. Overall, the capacity of L1 to adopt different coordination modes promotes the bimetallic C-C coupling channel through pathways that are unattainable with statically-coordinated ligands.

| S-EPMC8937615 | biostudies-literature

MRI-guided cell membrane-camouflaged bimetallic coordination nanoplatform for combined tumor phototherapy

Project description: Not available

| S-EPMC10950690 | biostudies-literature

Fabrication of an Active Electronic Device Using a Hetero-bimetallic Coordination Polymer.

Project description:A nickel(II)/lead(II) coordination polymer [(NCS)Pb(H2O)LNi(NCS)]n {H2L = N,N'-bis(3-methoxysalicylidene)propane-1,3-diamine} has been synthesized and characterized. The band gap (3.18 eV) calculated from Tauc's plot suggests the semiconducting nature of the complex. The material has a photosensitivity of 5.76, indicating its applicability in the fabrication of photosensitive devices. The complex has been successfully applied in a technologically challenging thin-film photosensitive Schottky device.

| S-EPMC6644615 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data