Browse
Submit Data
Databases
API
Help

Dataset Information

23 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Catalytic Hydrogenation of Cyclic Carbonates using Manganese Complexes.

ABSTRACT: Catalytic hydrogenation of cyclic carbonates to diols and methanol was achieved using a molecular catalyst based on earth-abundant manganese. The complex [Mn(CO)2 (Br)[HN(C2 H4 Pi Pr2 )2 ] 1 comprising commercially available MACHO ligand is an effective pre-catalyst operating under relatively mild conditions (T=120?°C, p(H2 )=30-60?bar). Upon activation with NaOt Bu, the formation of coordinatively unsaturated complex [Mn(CO)2 [N(C2 H4 Pi Pr2 )2 )] 5 was spectroscopically verified, which confirmed a kinetically competent intermediate. With the pre-activated complex, turnover numbers up to 620 and 400 were achieved for the formation of the diol and methanol, respectively. Stoichiometric reactions under catalytically relevant conditions provide insight into the stepwise reduction form the CO2 level in carbonates to methanol as final product.

SUBMITTER: Kaithal A

PROVIDER: S-EPMC6221167 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Catalytic Hydrogenation of Cyclic Carbonates using Manganese Complexes.

Kaithal Akash A Hölscher Markus M Leitner Walter W

Angewandte Chemie (International ed. in English) 20180912 41

Catalytic hydrogenation of cyclic carbonates to diols and methanol was achieved using a molecular catalyst based on earth-abundant manganese. The complex [Mn(CO)2 (Br)[HN(C2 H4 Pi Pr2 )2 ] 1 comprising commercially available MACHO ligand is an effective pre-catalyst operating under relatively mild conditions (T=120 °C, p(H2 )=30-60 bar). Upon activation with NaOt Bu, the formation of coordinatively unsaturate ...[more]

PMID: 30134081

Similar Datasets

A Neutral Heteroatomic Zintl Cluster for the Catalytic Hydrogenation of Cyclic Alkenes.

Project description:We report on the synthesis of an alkane-soluble Zintl cluster, [η4-Ge9(Hyp)3]Rh(COD), that can catalytically hydrogenate cyclic alkenes such as 1,5-cyclooctadiene and cis-cyclooctene. This is the first example of a well-defined Zintl-cluster-based homogeneous catalyst.

| S-EPMC7596751 | biostudies-literature

Non-Pincer-Type Manganese Complexes as Efficient Catalysts for the Hydrogenation of Esters.

Project description:Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub-stoichiometric amounts of KOt Bu base.

| S-EPMC5485043 | biostudies-literature

Fischer Carbene Complexes of Iridium(I) for Application in Catalytic Transfer Hydrogenation.

Project description:New examples of the very rare class of iridium(I) Fischer carbene complexes (FCCs) are reported from the facile transmetalation from group 6 FCCs. Postcomplexation modification of either the carbene ligand or the ancillary coligands results in a tunable IrI metal center, for unprecedented application as a (pre)catalyst in a benchmark transfer hydrogenation reaction. The introduction of an aminocarbene ligand with a pendant N-donor moiety capable of hemilabile coordination yielded the best catalytic results with turnover frequencies reaching 445 h-1 and requiring 0.1 mol % catalyst and 0.5 mol % base loading, respectively.

| S-EPMC7311058 | biostudies-literature

Exploring Oxidation State-Dependent Selectivity in Polymerization of Cyclic Esters and Carbonates with Zinc(II) Complexes.

Project description:Neutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ?-caprolactone, trimethylene carbonate, and ?-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and ?-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.

| S-EPMC6153418 | biostudies-literature

Selective Catalytic Synthesis of 1,2- and 8,9-Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes.

Project description:The selective catalytic synthesis of limonene-derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol-ene addition and amine ring-opening is reported. A phosphotungstate polyoxometalate catalyst used for limonene epoxidation in the 1,2-position is shown to also be active in cyclic carbonate synthesis, allowing a two-step, one-pot synthesis without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double-activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by-product formation in commercial mixtures of 1,2-limomene oxide. Carbonation of 8,9-limonene epoxide furnished the 8,9-limonene carbonate for the first time. Both cyclic carbonates underwent thiol-ene addition reactions to yield linked di-monocarbonates, which can be used in linear non-isocyanate polyurethanes synthesis, as shown by their facile ring-opening with N-hexylamine. Thus, the selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio-based polymers.

| S-EPMC7317810 | biostudies-literature

Metal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes.

Project description:A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

| S-EPMC7453403 | biostudies-literature

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts.

Project description:Alcohol-assisted hydrogenation of carbon monoxide (CO) to methanol was achieved using homogeneous molecular complexes. The molecular manganese complex [Mn(CO)2Br[HN(C2H4P i Pr2)2]] ([HN(C2H4P i Pr2)2] = MACHO- i Pr) revealed the best performance, reaching up to turnover number = 4023 and turnover frequency 857 h-1 in EtOH/toluene as solvent under optimized conditions (T = 150 °C, p(CO/H2) = 5/50 bar, t = 8-12 h). Control experiments affirmed that the reaction proceeds via formate ester as the intermediate, whereby a catalytic amount of base was found to be sufficient to mediate its formation from CO and the alcohol in situ. Selectivity for methanol formation reached >99% with no accumulation of the formate ester. The reaction was demonstrated to work with methanol as the alcohol component, resulting in a reactive system that allows catalytic "breeding" of methanol without any coreagents.

| S-EPMC8395606 | biostudies-literature

Versatile Catalytic Hydrogenation Using A Simple Tin(IV) Lewis Acid.

Project description:Despite the rapid development of frustrated Lewis pair (FLP) chemistry over the last ten years, its application in catalytic hydrogenations remains dependent on a narrow family of structurally similar early main-group Lewis acids (LAs), inevitably placing limitations on reactivity, sensitivity and substrate scope. Herein we describe the FLP-mediated H2 activation and catalytic hydrogenation activity of the alternative LA iPr3 SnOTf, which acts as a surrogate for the trialkylstannylium ion iPr3 Sn+ , and is rapidly and easily prepared from simple, inexpensive starting materials. This highly thermally robust LA is found to be competent in the hydrogenation of a number of different unsaturated functional groups (which is unique to date for main-group FLP LAs not based on boron), and also displays a remarkable tolerance to moisture.

| S-EPMC5129554 | biostudies-literature

Reactivity of Monovinyl (Meth)Acrylates Containing Cyclic Carbonates.

Project description:The tremendous diversity of materials properties available with polymers is due in large part to the ability to design structures from the monomeric state. The ease of use of comonomer mixtures only expands this versatility. While final polymer properties are obviously important in the selection or development of a material for a given purpose, for a number of applications, such as optical fiber coatings, photolithography and microelectronics, the additional requirement of a very rapid polymerization process may be equally critical. A class of unusually reactive mono-(meth)acrylate monomers bearing secondary functionality that includes carbonates, carbamates and oxazolidones, has been demonstrated but not fully explained. Here, the influence of an integral cyclic carbonate functional group on (meth)acrylate photopolymerization kinetics is examined in detail with respect to monomers with a wide variety of alternative secondary functionality structure as well as in comparison to conventional mono- and di-(meth)acrylates. The kinetic results from full cure studies of several cyclic carbonate-containing monomers clearly highlight specific structural variations that effectively promote monomer reactivity. Copolymerizations with tetrahydrofurfuryl methacrylate reflect similar dramatic kinetic effects associated with the novel monomers while partial cure homopolymerization studies reveal exceptional dark cure behavior linked to observations of uncommonly low ratios of termination to propagation rates throughout the conversion profile. Temperature effects on reaction kinetics, including both reaction rate and the individual kinetic parameters, as well as the temperature dependence of hydrogen bonding interactions specifically involving the secondary functional groups are probed as a means to understand better the fundamentally interesting and practically important behavior of these monomers.

| S-EPMC2764371 | biostudies-literature

Diversity-Oriented Metal Decoration on UiO-Type Metal-Organic Frameworks: an Efficient Approach to Increase CO2 Uptake and Catalytic Conversion to Cyclic Carbonates.

Project description:A library of metallo-bipyridine UiO-type metal-organic frameworks (MOFs) has been successfully synthesized by postmetallation of a wide range of metal complexes into bidentate bipyridine moieties. Then, a systematic investigation is devoted to a catalytic evaluation of the resultant MOFs containing a binary Lewis acid function for the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO2). The result indicated that the metal-grafted MOFs exhibit improvement in terms of CO2 uptake capacity and catalytic activity in comparison with their nonmetallated counterparts. The comprehensive investigation provides a valuable insight into the synergetic effects of MOF functionalities including metal node, grafted metal, and its counterion in the cycloaddition reaction. Furthermore, the metal coordination modulation due to its benefits such as being a solvent-free process, nearly full conversion to cyclic carbonates, high selectivity and high CO2 uptake, applying atmospheric CO2 pressure, and excellent stability and easy recyclability of the catalyst demonstrates them as promising candidates for practical utilization of CO2 conversion into value-added chemicals.

| S-EPMC6868879 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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