scholarly journals Iron-catalyzed hydrosilylation of CO2: CO2 conversion to formamides and methylamines

2014 ◽  
Vol 4 (6) ◽  
pp. 1529-1533 ◽  
Author(s):  
Xavier Frogneux ◽  
Olivier Jacquet ◽  
Thibault Cantat
Keyword(s):  
Iron Catalysts ◽  
Co2 Conversion ◽  
Reaction Conditions ◽  
Selective Approach ◽  
Catalytic Hydrosilylation

Catalytic hydrosilylation of CO2 is an efficient and selective approach to form chemicals. Herein, we describe the first iron catalysts able to promote the reductive functionalization of CO2 using hydrosilanes as reductants. Iron(ii) salts supported by phosphine donors enable the conversion of CO2 to formamide and methylamine derivatives under mild reaction conditions.

scholarly journals The COOL-Process—A Selective Approach for Recycling Lithium Batteries

Metals ◽  
2021 ◽  
Vol 11 (2) ◽  
pp. 259
Author(s):  
Sandra Pavón ◽  
Doreen Kaiser ◽  
Robert Mende ◽  
Martin Bertau
Keyword(s):  
Lithium Ion ◽  
Global Market ◽  
Raw Material ◽  
Mass Ratio ◽  
Reaction Conditions ◽  
Cool Process ◽  
Secondary Sources ◽  
Selective Approach ◽  
Valuable Metals ◽  
Housing Materials

The global market of lithium-ion batteries (LIB) has been growing in recent years, mainly owed to electromobility. The global LIB market is forecasted to amount to $129.3 billion in 2027. Considering the global reserves needed to produce these batteries and their limited lifetime, efficient recycling processes for secondary sources are mandatory. A selective process for Li recycling from LIB black mass is described. Depending on the process parameters Li was recovered almost quantitatively by the COOL-Process making use of the selective leaching properties of supercritical CO2/water. Optimization of this direct carbonization process was carried out by a design of experiments (DOE) using a 33 Box-Behnken design. Optimal reaction conditions were 230 °C, 4 h, and a water:black mass ratio of 90 mL/g, yielding 98.6 ± 0.19 wt.% Li. Almost quantitative yield (99.05 ± 0.64 wt.%), yet at the expense of higher energy consumption, was obtained with 230 °C, 4 h, and a water:black mass ratio of 120 mL/g. Mainly Li and Al were mobilized, which allows for selectively precipitating Li2CO3 in battery grade-quality (>99.8 wt.%) without the need for further refining. Valuable metals, such as Co, Cu, Fe, Ni, and Mn, remained in the solid residue (97.7 wt.%), from where they are recovered by established processes. Housing materials were separated mechanically, thus recycling LIB without residues. This holistic zero waste-approach allows for recovering the critical raw material Li from both primary and secondary sources.

Soldering of Iron Catalysts for Direct Synthesis of Light Olefins from Syngas under Mild Reaction Conditions

ACS Catalysis ◽  
2017 ◽  
Vol 7 (10) ◽  
pp. 6445-6452 ◽  
Author(s):  
Vitaly V. Ordomsky ◽  
Yuan Luo ◽  
Bang Gu ◽  
Alexandre Carvalho ◽  
Petr A. Chernavskii ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Light Olefins ◽  
Iron Catalysts ◽  
Reaction Conditions

scholarly journals The Application of Biomass-Based Catalytic Materials in the Synthesis of Cyclic Carbonates from CO2 and Epoxides

Molecules ◽  
2020 ◽  
Vol 25 (16) ◽  
pp. 3627 ◽  
Author(s):  
Li Guo ◽  
Ran Zhang ◽  
Yuge Xiong ◽  
Dandan Chang ◽  
Haoran Zhao ◽  
...  
Keyword(s):  
High Efficiency ◽  
Low Cost ◽  
Coupling Reaction ◽  
Catalytic Efficiency ◽  
Renewable Resource ◽  
Co2 Conversion ◽  
Cyclic Carbonates ◽  
Reaction Conditions ◽  
Co Catalysts ◽  
Carbon Dioxide Co2

The synthesis of cyclic carbonates from carbon dioxide (CO2) and epoxides is a 100% atom economical reaction and an attractive pathway for CO2 utilisation. Because CO2 is a thermodynamically stable molecule, the use of catalysts is mandatory in reducing the activation energy of the CO2 conversion. Considering environmental compatibility and the high-efficiency catalytic conversion of CO2, there is the strong need to develop green catalysts. Biomass-based catalysts, a type of renewable resource, have attracted considerable attention due to their unique properties—non-toxic, low-cost, pollution-free, etc. In this review, recent advances in the development of biomass-based catalysts for the synthesis of cyclic carbonates by CO2 and epoxides coupling are summarized and discussed in detail. The effect of biomass-based catalysts, functional groups, reaction conditions, and co-catalysts on the catalytic efficiency and selectivity of synthesizing cyclic carbonates process is discussed. We intend to provide a comprehensive understanding of recent experimental and theoretical progress of CO2 and epoxides coupling reaction and pave the way for both CO2 conversion and biomass unitization.

scholarly journals C-H Functionalization via Iron-Catalyzed Carbene-Transfer Reactions

Molecules ◽  
2020 ◽  
Vol 25 (4) ◽  
pp. 880 ◽  
Author(s):  
Claire Empel ◽  
Sripati Jana ◽  
Rene M. Koenigs
Keyword(s):  
Functional Groups ◽  
Organic Molecules ◽  
Transfer Reactions ◽  
Iron Catalysts ◽  
Reaction Conditions ◽  
Carbene Complexes ◽  
Small Organic Molecules ◽  
Iron Heme ◽  
Over Time ◽  
Functionalization Reaction

The direct C-H functionalization reaction is one of the most efficient strategies by which to introduce new functional groups into small organic molecules. Over time, iron complexes have emerged as versatile catalysts for carbine-transfer reactions with diazoalkanes under mild and sustainable reaction conditions. In this review, we discuss the advances that have been made using iron catalysts to perform C-H functionalization reactions with diazoalkanes. We give an overview of early examples employing stoichiometric iron carbene complexes and continue with recent advances in the C-H functionalization of C(sp2)-H and C(sp3)-H bonds, concluding with the latest developments in enzymatic C-H functionalization reactions using iron-heme-containing enzymes.

New Zinc Catalyst for Hydrosilylation of Carbonyl Compounds

Synthesis ◽  
2019 ◽  
Vol 51 (17) ◽  
pp. 3305-3312 ◽  
Author(s):  
Iryna D. Alshakova ◽  
Georgii I. Nikonov
Keyword(s):  
Carbonyl Compounds ◽  
Zinc Complex ◽  
Allylic Alcohols ◽  
Reaction Conditions ◽  
Unsaturated Aldehydes ◽  
Substoichiometric Amount ◽  
Aldehydes And Ketones ◽  
Catalytic Hydrosilylation ◽  
Catalyst Load

A new zinc complex was synthesized and applied in the catalytic hydrosilylation of carbonyl compounds. Optimization of the reaction conditions showed that the presence a substoichiometric amount of methanol accelerates the process significantly. The reaction can proceed at very low catalyst load (down to 0.1 mol%) under mild reaction conditions. The reaction tolerates the presence of C=C bonds, and thus can be useful for the synthesis of allylic alcohols from α,β-unsaturated aldehydes and ketones.

Synthesis and Molecular Structure of Silylated Ethenes and Acetylenes

1994 ◽  
Vol 49 (10) ◽  
pp. 1348-1360 ◽  
Author(s):  
Christoph Rüdinger ◽  
Holger Beruda ◽  
Hubert Schmidbaur
Keyword(s):  
Molecular Structure ◽  
Reductive Elimination ◽  
Molecular Structures ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Reaction Conditions ◽  
X Ray ◽  
Space Groups ◽  
Crystal And Molecular Structures ◽  
Catalytic Hydrosilylation

AbstractDisilylacetylene (1) has been obtained from LiAlH4 reduction of bis(trichlorosilyl)acetylene (2) and bis[(trifluoromethylsulfonyloxy)silyl]acetylene (4). The catalytic hydrosilylation of 2 with HSiCl3 affords tris(trichlorosilyl)ethene (5) and 1.1.2-tris(trichlorosilyl)ethane (6). The synthesis of 6, trans-bis(trichlorosilyl)ethene (8) and 1,1-bis(trichlorosilyl)ethene (9) has been accomplished by hydrosilyiation of trichlorosilylacetylene (7) which was synthesized by the reaction of trichloro(trifluoromethylsulfonyloxy)silane with sodium acetylide. Reductive elimination of halogen from 1,1,1,2-tetrachloro-bis(trichlorosilyl)ethane (10) and 1,2- dibromo-1,1-bis(trichlorosiIyl)ethane (13) gave the corresponding ethenes 1,1-dichloro-bis- (trichlorosilyl)ethene (11), trichloro-trichlorosilylethene (12), 1,1-bis(trichlorosilyl)ethene (9) and 1-chloro-2,2-bis(trichlorosilyl)ethene (14). Tetrakis(trichlorosilyl)ethene (15) has been obtained in a three step synthesis starting from chloromethyl-trichlorosilane or dichloro- methyl-trichlorosilane. By LiAlH4 reduction of trichlorosilylethenes under various reaction conditions, the silylethenes trans-dichloro-di(silyl)ethene (16), 1,1-dichloro-di(silyl)ethene (17), trichloro-silylethene (18), 1-bromo-l-silylethene (19), trans-di(silyl)ethene (20), 1-chloro-2,2-di(silyl)ethene (21), tri(silyl)ethene (22) and 1,1,2-tri(silyl)ethane (23) could be generated. Silylethyne and silyl-chloroethyne were identified as side products. The crystal and molecular structures of 2,5 and 15 have been determined by single crystal X-ray diffraction. 2 and 5 crystallize from the melt in the monoclinic space groups Cc and P21/n, respectively. 15 has been crystallized by sublimation (orthorhombic. space group Pbca). 5 and 15 feature strongly distorted ethene skeletons with a double bond twist of 28.1° in 15.

The changes caused by activation and reaction conditions on the morphology of iron catalysts

1994 ◽  
Vol 52 ◽  
pp. 778-779
Author(s):  
D. S. Kalakkad ◽  
M. Shroff ◽  
A. K. Datye
Keyword(s):  
Electron Microscopy ◽  
Transmission Electron Microscopy ◽  
Carbon Deposition ◽  
Low Cost ◽  
Iron Catalysts ◽  
Synthetic Fuels ◽  
Fischer Tropsch ◽  
Reaction Conditions ◽  
Transmission Electron ◽  
Fe Catalysts

Iron is considered to be one of the most active/low cost catalysts for Fischer-Tropsch synthesis (FTS) used to produce higher order hydrocarbons and synthetic fuels from coal. One of the biggest obstacles faced by the industry in the use of iron is that of rapid deactivation and attrition. While it is generally accepted that deactivation occurs due to carbon deposition or “coking”, the actual steps involved in the formation and deposition of carbon have not yet been thoroughly understood. Also, the causes for attrition in these catalysts have not yet been established.Our present study involves use of transmission electron microscopy to find the effect of various pretreatment and reaction conditions on the microstructure of Fe catalysts and scanning electron microscopy to study the problem of attrition. The transmission electron microscopy was performed on a 200 kVJEOL JEM 2000FX microscope and the SEM was done using a Hitachi S800 microscope.

scholarly journals Sustainable catalytic rearrangement of terpene-derived epoxides: towards bio-based biscarbonyl monomers

2020 ◽  
Vol 378 (2176) ◽  
pp. 20190267
Author(s):  
P. S. Löser ◽  
P. Rauthe ◽  
M. A. R. Meier ◽  
A. Llevot
Keyword(s):  
Renewable Resources ◽  
Lewis Acids ◽  
Catalyst Loading ◽  
Chemical Transformations ◽  
Reaction Conditions ◽  
Selective Approach ◽  
Limonene Oxide ◽  
Bismuth Triflate ◽  
Low Catalyst Loading ◽  
Elementary Chemical

Seeking a sustainable and selective approach for terpene modification, a catalyst deconvolution approach was applied to the Meinwald rearrangement of (+)-limonene oxide as a model substrate to yield dihydrocarvone. In order to identify the most suitable catalyst and reaction conditions, different Lewis acids were evaluated. Bismuth triflate proved to be the most active catalyst under mild reaction conditions, with a low catalyst loading (1 mol%) and a relatively short reaction time (3 h). The optimized reaction conditions were subsequently transferred to other terpene-based epoxides, yielding different bio-based biscarbonyl structures, which constitute interesting and valuable substances, e.g. for polymer synthesis or as fragrances. Monoepoxides derived from ( R )-(−)-carvone and (+)-dihydrocarvone rearranged to the desired products with high selectivities and yields. γ-Terpinene dioxide could be transformed in a double rearrangement to the respective biscarbonyl in moderate yields. A better result was achieved for limonene dioxide after further adjustment of the protocol to reach acceptable yields with a low catalyst loading of 0.1 mol% using 2-methyl tetrahydrofuran as a sustainable solvent. Compared to many procedures described in the literature, this procedure represents a step towards an increased sustainability in terpene modification by considering several principles of Green Chemistry, such as renewable resources, catalysis and mild reaction conditions for elementary chemical transformations. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.

Organic nanocages: a promising testbed for catalytic CO2 conversion

2019 ◽  
Vol 3 (10) ◽  
pp. 2567-2571 ◽  
Author(s):  
MD. Waseem Hussain ◽  
Arkaprabha Giri ◽  
Abhijit Patra
Keyword(s):  
Solvent Free ◽  
Co2 Conversion ◽  
Reaction Conditions ◽  
Metal Free ◽  
Organic Carbonates ◽  
Solvent Free Reaction

Shape-persistent N-rich organic cages are demonstrated as catalysts for the metal-free conversion of CO2 and epoxides into cyclic organic carbonates under solvent-free reaction conditions.

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