Dataset Information

Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO₂ Fixation in a Metal-Organic Framework.

ABSTRACT: Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO₂ in the presence of H₂ over a metal-organic framework supported ruthenium catalyst, Ru/MFM-300(Cr). Highly selective production of N-formamides has been observed for a wide range of carbonyl compounds. Synchrotron X-ray powder diffraction reveals the presence of strong host-guest binding interactions via hydrogen bonding and parallel-displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO₂ utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.

SUBMITTER: Huang W

PROVIDER: S-EPMC10952134 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal-Organic Framework.

Huang Wenyuan W Mei Qingqing Q Xu Shaojun S An Bing B He Meng M Li Jiangnan J Chen Yinlin Y Han Xue X Luo Tian T Guo Lixia L Hurd Joseph J Lee Daniel D Tillotson Evan E Haigh Sarah J SJ Walton Alex A Day Sarah J SJ Natrajan Louise S LS Schröder Martin M Yang Sihai S

Chemistry (Weinheim an der Bergstrasse, Germany) 20231212 7

Formamides are important feedstocks for the manufacture of many fine chemicals. State-of-the-art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom-economy. Here, we report the first example of direct synthesis of N-formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass-derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over ...[more]

PMID: 37899311

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Project description:Precisely locating extra-framework cations in anionic metal-organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure-performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal-organic framework Fe2(bdp)3 (bdp2- = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A2Fe2(bdp)3·yTHF (A = Li+, Na+, K+). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation-π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na0.5Fe2(bdp)3 and Li2Fe2(bdp)3 and the first structural characterization of activated metal-organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation-π interactions. Hydrogen adsorption data indicate that these cation-framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe2(bdp)3. In contrast, Mg0.85Fe2(bdp)3 exhibits enhanced H2 affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation-framework interactions and thereby promotes stronger cation-H2 interactions.

Dataset Information

Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO₂ Fixation in a Metal-Organic Framework.

Publications

Direct Synthesis of N-formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO<sub>2</sub> Fixation in a Metal-Organic Framework.

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