Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Unprecedent formation of methylsilylcarbonates from iridium-catalyzed reduction of CO₂ with hydrosilanes.

ABSTRACT: The iridium complex [Ir(μ-CF₃SO₃)(κ²-NSi^Me2)₂]₂ (3) (NSi^Me2 = {4-methylpyridine-2-yloxy}dimethylsilyl) has been prepared by reaction of [Ir(μ-Cl)(κ²-NSi^Me2)₂]₂ (1) with two equivalents of AgCF₃SO₃. The solid structure of 3 evidenced its dinuclear nature, being a rare example of an iridium species with triflate groups acting as bridges. The 3-catalyzed reduction of CO₂ with HSiMe(OSiMe₃)₂ affords a mixture of the corresponding silylformate and methoxysilane together with the silylcarbonate CH₃OCO₂SiMe(OSiMe₃)₂ (4a). This is the first time that the formation of silylcarbonates has been observed from the catalytic reduction of CO₂ with silanes. Analogous behaviour has been observed when HSiMe₂Ph and HSiMePh₂ were used as reductants.

SUBMITTER: Guzman J

PROVIDER: S-EPMC9050147 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Unprecedent formation of methylsilylcarbonates from iridium-catalyzed reduction of CO2 with hydrosilanes.

Guzmán Jefferson J García-Orduña Pilar P Lahoz Fernando J FJ Fernández-Alvarez Francisco J FJ

RSC advances 20200305 16

The iridium complex [Ir(μ-CF3SO3)(κ2-NSiMe2)2]2 (3) (NSiMe2 = {4-methylpyridine-2-yloxy}dimethylsilyl) has been prepared by reaction of [Ir(μ-Cl)(κ2-NSiMe2)2]2 (1) with two equivalents of AgCF3SO3. The solid structure of 3 evidenced its dinuclear nature, being a rare example of an iridium species with triflate groups acting as bridges. The 3-catalyzed red ...[more]

PMID: 35497254

Similar Datasets

Reductive Deamination with Hydrosilanes Catalyzed by B(C6 F5 )3.

Project description:The strong boron Lewis acid tris(pentafluorophenyl)borane B(C6 F5 )3 is known to catalyze the dehydrogenative coupling of certain amines and hydrosilanes at elevated temperatures. At higher temperature, the dehydrogenation pathway competes with cleavage of the C-N bond and defunctionalization is obtained. This can be turned into a useful methodology for the transition-metal-free reductive deamination of a broad range of amines as well as heterocumulenes such as an isocyanate and an isothiocyanate.

| S-EPMC7384015 | biostudies-literature

Mechanism Insights into the Iridium(III)- and B(C6F5)3-Catalyzed Reduction of CO2 to the Formaldehyde Level with Tertiary Silanes.

Project description:The catalytic system [Ir(CF3CO2)(κ2-NSiMe)2] [1; NSiMe = (4-methylpyridin-2-yloxy)dimethylsilyl]/B(C6F5)3 promotes the selective reduction of CO2 with tertiary silanes to the corresponding bis(silyl)acetal. Stoichiometric and catalytic studies evidenced that species [Ir(CF3COO-B(C6F5)3)(κ2-NSiMe)2] (3), [Ir(κ2-NSiMe)2][HB(C6F5)3] (4), and [Ir(HCOO-B(C6F5)3)(κ2-NSiMe)2] (5) are intermediates of the catalytic process. The structure of 3 has been determined by X-ray diffraction methods. Theoretical calculations show that the rate-limiting step for the 1/B(C6F5)3-catalyzed hydrosilylation of CO2 to bis(silyl)acetal is a boron-promoted Si-H bond cleavage via an iridium silylacetal borane adduct.

| S-EPMC10468102 | biostudies-literature

Light-driven carbon-carbon bond formation via CO2 reduction catalyzed by complexes of CdS nanorods and a 2-oxoacid oxidoreductase.

Project description:Redox enzymes are capable of catalyzing a vast array of useful reactions, but they require redox partners that donate or accept electrons. Semiconductor nanocrystals provide a mechanism to convert absorbed photon energy into redox equivalents for enzyme catalysis. Here, we describe a system for photochemical carbon-carbon bond formation to make 2-oxoglutarate by coupling CO2 with a succinyl group. Photoexcited electrons from cadmium sulfide nanorods (CdS NRs) transfer to 2-oxoglutarate:ferredoxin oxidoreductase from Magnetococcus marinus MC-1 (MmOGOR), which catalyzes a carbon-carbon bond formation reaction. We thereby decouple MmOGOR from its native role in the reductive tricarboxylic acid cycle and drive it directly with light. We examine the dependence of 2-oxoglutarate formation on a variety of factors and, using ultrafast transient absorption spectroscopy, elucidate the critical role of electron transfer (ET) from CdS NRs to MmOGOR. We find that the efficiency of this ET depends strongly on whether the succinyl CoA (SCoA) cosubstrate is bound at the MmOGOR active site. We hypothesize that the conformational changes due to SCoA binding impact the CdS NR-MmOGOR interaction in a manner that decreases ET efficiency compared to the enzyme with no cosubstrate bound. Our work reveals structural considerations for the nano-bio interfaces involved in light-driven enzyme catalysis and points to the competing factors of enzyme catalysis and ET efficiency that may arise when complex enzyme reactions are driven by artificial light absorbers.

| S-EPMC6955356 | biostudies-literature

Mechanistic insights into reductive deamination with hydrosilanes catalyzed by B(C6F5)3: A DFT study.

Project description:Selective defunctionalization of synthetic intermediates is a valuable approach in organic synthesis. Here, we present a theoretical study on the recently developed B(C6F5)3/hydrosilane-mediated reductive deamination reaction of primary amines. Our computational results provide important insights into the reaction mechanism, including the active intermediate, the competing reactions of the active intermediate, the role of excess hydrosilane, and the origin of chemoselectivity. Moreover, the study on the substituent effect of hydrosilane indicated a potential way to improve the efficiency of the reductive deamination reaction.

| S-EPMC9709212 | biostudies-literature

Iridium-Catalyzed C-H Borylation of CF3-Substituted Pyridines.

Project description:Iridium-catalyzed C-H borylation of CF3-substituted pyridines is described in this paper. The boronic ester group can be installed on the α, β, or γ position of pyridine by an appropriate substitution pattern. Sterically governed regioselectivity provides convenient access to a variety of CF3-substituted pyridylboronic esters. These catalytic C-H borylation reactions were carried out neatly without the use of any solvent. Several functional groups, such as halo, ester, alkoxy, amino, etc., are compatible with this methodology. These pyridylboronic esters are amenable to column chromatography and the products were isolated in good to excellent yields. α-Borylated pyridines, although isolated in good yields, do not have a long shelf life. The boronic ester derivatives of these CF3-substituted pyridines can serve as useful precursors in the synthesis regime.

| S-EPMC8992268 | biostudies-literature

Computational Study of the Ir-Catalyzed Formation of Allyl Carbamates from CO2.

Project description:We have employed computational methods to investigate the iridium-catalyzed allylic substitution leading to the formation of enantioenriched allyl carbamates from carbon dioxide (CO2). The reaction occurs in several steps, with initial formation of an iridium-allyl, followed by nucleophilic attack by the carbamate formed in situ from CO2 and an amine. A detailed isomeric analysis shows that the rate-determining step differs for the (R)- and (S)-pathways. These insights are essential for understanding reactions involving enantioselective formation of allyl carbamates from CO2.

| S-EPMC11388460 | biostudies-literature

Iridium-Catalyzed Highly Selective 1,4-Reduction of α,β-Unsaturated Carbonyl Compounds

Project description: Not available

| S-EPMC11678408 | biostudies-literature

Enantioselective Iridium-Catalyzed Phthalide Formation through Internal Redox Allylation of Phthalaldehydes.

Project description:An inside job: Enantioselective phthalide synthesis was achieved through internal redox allylation of o-phthalaldehydes. Oxidative esterification is balanced by reductive carbonyl addition to achieve an overall redox-neutral process. This method enabled formal syntheses of ent-spirolaxine methyl ether and CJ-12,954.

| S-EPMC5777894 | biostudies-literature

Enantioselective Formation of CF3-Bearing All-Carbon Quaternary Stereocenters via C-H Functionalization of Methanol: Iridium Catalyzed Allene Hydrohydroxymethylation.

Project description:Using an iridium catalyst modified by PhanePhos, CF3-allenes react with methanol to form branched products of hydrohydroxymethylation as single regioisomers with excellent levels of enantiomeric enrichment. This hydrogen autotransfer process enables catalytic enantioselective formation of acyclic CF3-bearing all-carbon quaternary stereocenters in the absence of stoichiometric metals or byproducts.

| S-EPMC5651675 | biostudies-literature

Self-sensitized Cu(ii)-complex catalyzed solar driven CO2 reduction.

Project description:Developing a self-sensitized catalyst from earth-abundant elements, capable of efficient light harvesting and electron transfer, is crucial for enhancing the efficacy of CO2 transformation, a critical step in environmental cleanup and advancing clean energy prospects. Traditional approaches relying on external photosensitizers, comprising 4d/5d metal complexes, involve intermolecular electron transfer, and attachment of photosensitizing arms to the catalyst necessitates intramolecular electron transfer, underscoring the need for a more integrated solution. We report a new Cu(ii) complex, K[CuNDPA] (1[K(18-crown-6)]), bearing a dipyrrin amide-based trianionic tetradentate ligand, NDPA (H3L), which is capable of harnessing light energy, despite having a paramagnetic Cu(ii) centre, without any external photosensitizer and photocatalytically reducing CO2 to CO in acetonitrile : water (19 : 1 v/v) with a TON as high as 1132, a TOF of 566 h-1 and a selectivity of 99%. This complex also shows hemilability in the presence of water, which not only plays a role in the proton relay mechanism but also helps stabilize a crucial Cu(i)-NDPA intermediate. The hemilability was justified by the formation of N3O (2) and N2O2 (3) coordinated congeners of the N4 bound complex 1. The overall mechanism was further investigated via spectroscopic techniques such as EPR, UV-vis, and spectroelectrochemistry, culminating in the justification of a single electron-reduced Cu(i)NDPA species as a proposed intermediate. In the next step, the binding of CO2 to the Cu(i) complex and subsequent electron transfer to form Cu(ii)-COO·- was indirectly probed by a radical trapping experiment via the addition of p-methoxy-2,6-di-tert-butylphenol that led to the formation of a phenoxyl radical. This work provides new strategies for designing earth-abundant robust molecular catalysts that can function as photocatalysts without the aid of any external photosensitizers.

| S-EPMC11736929 | biostudies-literature