Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Generation and Reactions of a Benzodehydrotropylium Ion-Co₂(CO)₆ Complex.

ABSTRACT: A series of 7-methylenedehydrobenzo[7]annulen-5-ol hexacarbonyldicobalt complexes were generated by Hosomi-Sakurai reactions of allylsilanes containing o-alkynylarylaldehyde-Co₂(CO)₆ complexes. One of the cyclization products was converted into its corresponding dihydrobenzo[7]annulen-7-ol hexacarbonyldicobalt complex, an immediate precursor to a benzodehydrotropylium-Co₂(CO)₆. The cation was generated in situ and reacted with four nucleophiles, and its aromatic stabilization was determined by computational methods.

SUBMITTER: Mehdi MA

PROVIDER: S-EPMC6854560 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Generation and Reactions of a Benzodehydrotropylium Ion-Co2(CO)6 Complex.

Mehdi Mariam A MA Bushnell Eric A C EAC Nikoo Sahar S Gauld James W JW Green James R JR

ACS omega 20191028 20

A series of 7-methylenedehydrobenzo[7]annulen-5-ol hexacarbonyldicobalt complexes were generated by Hosomi-Sakurai reactions of allylsilanes containing o-alkynylarylaldehyde-Co2(CO)6 complexes. One of the cyclization products was converted into its corresponding dihydrobenzo[7]annulen-7-ol hexacarbonyldicobalt complex, an immediate precursor to a benzodehydrotropylium-Co2(CO)6. The cation was generated in situ and reacted with four nucleophiles, ...[more]

PMID: 31737819

Similar Datasets

The Generation of Dehydroalanine Residues in Protonated Polypeptides: Ion/Ion Reactions for Introducing Selective Cleavages.

Project description:We examine a gas-phase approach for converting a subset of amino acid residues in polypeptide cations to dehydroalanine (Dha). Subsequent activation of the modified polypeptide ions gives rise to specific cleavage N-terminal to the Dha residue. This process allows for the incorporation of selective cleavages in the structural characterization of polypeptide ions. An ion/ion reaction within the mass spectrometer between a multiply protonated polypeptide and the sulfate radical anion introduces a radical site into the multiply protonated polypeptide reactant. Subsequent collisional activation of the polypeptide radical cation gives rise to radical side chain loss from one of several particular amino acid side chains (e.g., leucine, asparagine, lysine, glutamine, and glutamic acid) to yield a Dha residue. The Dha residues facilitate preferential backbone cleavages to produce signature c- and z-ions, demonstrated with cations derived from melittin, mechano growth factor (MGF), and ubiquitin. The efficiencies for radical side chain loss and for subsequent generation of specific c- and z-ions have been examined as functions of precursor ion charge state and activation conditions using cations of ubiquitin as a model for a small protein. It is noted that these efficiencies are not strongly dependent on ion trap collisional activation conditions but are sensitive to precursor ion charge state. Moderate to low charge states show the greatest overall yields for the specific Dha cleavages, whereas small molecule losses (e.g., water/ammonia) dominate at the lowest charge states and proton catalyzed amide bond cleavages that give rise to b- and y-ions tend to dominate at high charge states. Graphical Abstract ?.

| S-EPMC5681889 | biostudies-literature

Reactions of CO2 and ethane enable CO bond insertion for production of C3 oxygenates.

Project description:Reacting CO2 and ethane to synthesize value-added oxygenate molecules represents opportunities to simultaneously reduce CO2 emissions and upgrade underutilized ethane in shale gas. Herein, we propose a strategy to produce C3 oxygenates using a tandem reactor. This strategy is achieved with a Fe3Ni1/CeO2 catalyst (first reactor at 600-800?°C) for CO2-assisted dehydrogenation and reforming of ethane to produce ethylene, CO, and H2, and a RhCox/MCM-41 catalyst (second reactor at 200?°C) enabling CO insertion for the production of C3 oxygenates (propanal and 1-propanol) via the heterogeneous hydroformylation reaction at ambient pressure. In-situ characterization using synchrotron spectroscopies and density functional theory (DFT) calculations reveal the effect of Rh-Co bimetallic formation in facilitating the production of C3 oxygenates. The proposed strategy provides an opportunity for upgrading light alkanes in shale gas by reacting with CO2 to produce aldehydes and alcohols.

| S-EPMC7170877 | biostudies-literature

Mechanochemical Grignard Reactions with Gaseous CO2 and Sodium Methyl Carbonate.

Project description:A one-pot, three-step protocol for the preparation of Grignard reagents from organobromides in a ball mill and their subsequent reactions with gaseous carbon dioxide (CO2 ) or sodium methyl carbonate providing aryl and alkyl carboxylic acids in up to 82 % yield is reported. Noteworthy are the short reaction times and the significantly reduced solvent amounts [2.0 equiv. for liquid assisted grinding (LAG) conditions]. Unexpectedly, aryl bromides with methoxy substituents lead to symmetric ketones as major products.

| S-EPMC9306648 | biostudies-literature

Generation of Multiply Charged Protein Anions from Multiply Charged Protein Cations via Gas-Phase Ion/Ion Reactions.

Project description:We report a novel charge inversion ion/ion reaction that converts multiply charged protein cations to multiply charged protein anions via a single ion/ion collision using highly charged anions derived from nanoelectrospray ionization (nESI) of hyaluronic acids (HAs). This type of charge inversion reaction is demonstrated with cations derived from cytochrome c, apo-myoglobin, and carbonic anhydrase (CA) cations. For example, the reaction has been demonstrated to convert the [CA+22H]22+ carbonic anhydrase cation to a distribution of anions as high in absolute charge as [CA-19H]19-. Ion/ion reactions involving multiply charged ions of opposite polarity have previously been observed to result predominantly in the attachment of the reactant ions. All mechanisms for ion/ion charge inversion involving low energy ions proceed via the formation of a long-lived complex. Factors that underlie the charge inversion of protein cations to high anionic charge states in reaction with HA anions are hypothesized to include: (i) the relatively high charge densities of the HA anions that facilitate the extraction of multiple protons from the protein leading to multiply charged protein anions, (ii) the relatively high sum of absolute charges of the reactants that leads to high initial energies in the ion/ion complex, and (iii) the relatively high charge of the ion/ion complex following the multiple proton transfers that tends to destabilize the complex.

| S-EPMC7332380 | biostudies-literature

Structural Evolution of Ga-Cu Model Catalysts for CO2 Hydrogenation Reactions.

Project description:We studied the initial stages of Ga interaction with the Cu(001) surface and environment-induced surface transformations in an attempt to elucidate the surface chemistry of the Cu-Ga catalysts recently proposed for CO2 hydrogenation to methanol. The results show that Ga readily intermixes with Cu upon deposition in vacuum. However, even traces of oxygen in the gas ambient cause Ga oxidation and the formation of two-dimensional ("monolayer") Ga oxide islands uniformly covering the Cu surface. The surface morphology and the oxidized state of Ga remain in H2 as well as in a CO2 + H2 reaction mixture at elevated pressures and temperatures (0.2 mbar, 700 K). The results indicate that the Ga-doped Cu surface under reaction conditions exposes a variety of structures including GaO x /Cu interfacial sites, which must be taken into account for elucidating the reaction mechanism.

| S-EPMC7830109 | biostudies-literature

Bifunctional organoboron-phosphonium catalysts for coupling reactions of CO2 and epoxides.

Project description:Recent years have witnessed intensive research activity in exploring novel metal-free organocatalysts for catalyzing the coupling reactions of CO2 and epoxides to afford cyclic or polymeric carbonates. In this direction, herein we report a series of boron-phosphonium organocatalysts for catalyzing the coupling reactions of CO2 and epoxides. These organophosphonium catalysts were synthesized in high yields by following a two step protocol involving Menschutkin and hydroboration reactions in succession. The purity of these organocatalysts was confirmed by spectroscopic techniques like 1H, 13C and 31P NMR, and molecular structures were confirmed by single crystal X-ray diffraction studies. We have also demonstrated that these bifunctional organoboron-phosphonium catalysts are comparatively much less hygroscopic compared to the analogus ammonium catalysts. These phosphonium organocatalysts were shown to catalyze the copolymerization of CO2 and cyclohexene oxide or vinyl cyclohexene oxide to provide polycarbonates with >99% polymer selectivity and carbonate linkages. The coupling reactions of aliphatic epoxides such as PO, having lower energy barrier to cycloaddition formation compared to alicyclic epoxides, preferentially provided cyclic carbonates in good yields. It was demonstrated that these organoboron-phosphonium catalysts are sensitive to chain transfer agents like water, and hence are deactivated in its presence. This is opposite to what is observed for metal based catalysts for these transformations, where water serves as a precursor to the chain-transfer agent diols.

| S-EPMC9661183 | biostudies-literature

Engineering Photothermal Catalytic CO2 Nanoreactor for Osteomyelitis Treatment by In Situ CO Generation.

Project description:Photocatalytic carbon dioxide (CO2) reduction is an effective method for in vivo carbon monoxide (CO) generation for antibacterial use. However, the available strategies mainly focus on utilizing visible-light-responsive photocatalysts to achieve CO generation. The limited penetration capability of visible light hinders CO generation in deep-seated tissues. Herein, a photothermal CO2 catalyst (abbreviated as NNBCs) to achieve an efficient hyperthermic effect and in situ CO generation is rationally developed, to simultaneously suppress bacterial proliferation and relieve inflammatory responses. The NNBCs are modified with a special polyethylene glycol and further embellished by bicarbonate (BC) decoration via ferric ion-mediated coordination. Upon exposure to 1064 nm laser irradiation, the NNBCs facilitated efficient photothermal conversion and in situ CO generation through photothermal CO2 catalysis. Specifically, the photothermal effect accelerated the decomposition of BC to produce CO2 for photothermal catalytic CO production. Benefiting from the hyperthermic effect and in situ CO production, in vivo assessments using an osteomyelitis model confirmed that NNBCs can simultaneously inhibit bacterial proliferation and attenuate the photothermal effect-associated pro-inflammatory response. This study represents the first attempt to develop high-performance photothermal CO2 nanocatalysts to achieve in situ CO generation for the concurrent inhibition of bacterial growth and attenuation of inflammatory responses.

| S-EPMC11220635 | biostudies-literature

Co-Precipitation Synthesis of Co3[Fe(CN)6]2·10H2O@rGO Anode Electrode for Lithium-Ion Batteries.

Project description:Rechargeable lithium-ion batteries (LIBs) are known to be practical and cost-effective devices for storing electric energy. LIBs have a low energy density, which calls for the development of new anode materials. The Prussian blue analog (PBA) is identified as being a candidate electrode material due to its facile synthesis, open framework structures, high specific surface areas, tunable composition, designable topologies and rich redox couples. However, its poor electrical conductivity and mechanical properties are the main factors limiting its use. The present study loaded PBA (Co3[Fe(CN)6]·10H2O) on graphene oxide (Co-Fe-PBA@rGO) and then conducted calcination at 300 °C under the protection of nitrogen, which reduced the crystal water and provided more ion diffusion pathways. As a result, Co-Fe-PBA@rGO showed excellent performance when utilized as an anode in LIBs, and its specific capacities were 546.3 and 333.2 mAh g-1 at 0.1 and 1.0 A g-1, respectively. In addition, the electrode also showed excellent performance in the long-term cycle, and its capacity reached up to 909.7 mAh g-1 at 0.1 A g-1 following 100 cycles.

| S-EPMC9267929 | biostudies-literature

Reactions of [Fe6C(CO)14(S)]2-: Cluster Growth, Redox, Sulfiding.

Project description:Redox reactions, substitutions, and metalations are reported for the iron carbido sulfide [Fe6C(CO)14(S)]2- ([1]2-). Dianion [1]2- oxidized to [Fe6C(CO)16(S)]0 ([2]0) upon treatment with of [Fe(C5H5)2]BF4 or HBF4 (H2 formation) under an atmosphere of CO. Reaction of [2]0 with tBuNC gave [Fe6C(S)(CO)13(tBuNC)5], consisting of Fe5C(CO)13 and [Fe(tBuNC)5]2+ subunits linked by a μ3-S2-. The Fe7CS cluster [Fe7C(CO)17(S)]2- formed upon treatment of (Ph4P)2[1] with Fe(benzylideneacetone)(CO)3. The Fe7 species is an edge-fused cluster with [Fe6C(CO)10(μ-CO)4] and Fe(CO)3 subunits joined by μ3-S and two Fe-Fe bonds. The analogous reaction using Mo(CO)4(norbornadiene) gave [MoFe6C(CO)18(S)]2-. In this cluster, the Mo center is located in the octahedral subunit. Treatment of [1]2- with SO2 afforded [Fe6C(S)(SO2)(CO)13]2-. This cluster features an Fe6C core decorated with μ3-S and μ2-SO2 ligands. These experiments were undertaken in an effort to connect organometallic clusters to FeMoco.

| S-EPMC8054992 | biostudies-literature

Ultrathin Mesoporous Co3O4 Nanosheet Arrays for High-Performance Lithium-Ion Batteries.

Project description:Transition metal oxides, such as Co3O4, have attracted great attention for lithium-ion batteries (LIBs) due to their high theoretical capacity and satisfactory chemical stability. However, the slow kinetics of Li-ion and electron transport as well as poor cycling stability still largely restrains their applications. Here, we report the rational design of well-defined mesoporous ultrathin Co3O4 nanosheet arrays (NSAs) by topological transformation of layered double hydroxides nanosheet arrays (NSAs), which demonstrate significantly enhanced performance as anode for LIBs. The as-obtained Co3O4 NSAs with suitable thickness and abundant mesopores show excellent electrochemistry performance for LIBs, giving a high specific charge capacity of 2019.6 mAh g-1 at 0.1 A g-1, a good rate capability, and a remarkable cycling stability (1576.9 mAh g-1 after the 80th cycle), which is much superior to that of Co3O4 with thicker or thinner nanosheets as well as to that of the reported results. This facile strategy may be extended to the synthesis of other transition metal oxide NSAs, which can be potentially used in energy storage and conversion devices.

| S-EPMC6641328 | biostudies-literature