Recent progress in ammonia synthesis based on photoelectrocatalysis

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(16), P. 4650 - 4667

Published: Jan. 1, 2023

Photoelectrocatalytic NH 3 synthesis from N 2 and H O is a promising approach for N-neutralization goal based on catalytic strategies, such as vacancy engineering, ion doping, frustrated Lewis pair design, heterojunction construction, etc .

Language: Английский

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An orbitally adapted push–pull template for N₂ activation and reduction to diazene-diide

Chemical Science, Journal Year: 2023, Volume and Issue: 14(48), P. 14262 - 14270

Published: Jan. 1, 2023

A Lewis superacidic bis(borane) C6F4{B(C6F5)2}2 was reacted with tungsten N2-complexes [W(N2)2(R2PCH2CH2PR2)2] (R = Ph or Et), affording zwitterionic boryldiazenido W(ii) complexes trans-[W(L)(R2PCH2CH2PR2)2(N2{B(C6F5)2(C6F4B(C6F5)3})] (L ø, N2 THF). These compounds feature only one N-B linkage of the covalent type, as a result intramolecular boron-to-boron C6F5 transfer. Complex trans-[W(THF)(Et2PCH2CH2PEt2)2(N2{B(C6F5)2C6F4B(C6F5)3})] (5) shown to split H2, leading seven-coordinate complex [W(H)2(Et2PCH2CH2PEt2)2(N2{B(C6F5)2}2C6F4)] (7). Interestingly, hydride storage at metal triggers backward This reverts bis(boron) moiety its state, now doubly binding distal N, structural parameters and DFT computations pointing dative N→B bonding. By comparison an [W(H)2(Et2PCH2CH2PEt2)2(N2{B(C6F5)3}] (10) differing in acid (LA), namely B(C6F5)3, coordinated we demonstrate that two-fold LA coordination imparts strong activation up diazene-diide (N22-) state. To best our knowledge, this is first example neutral induces reduction N2.

Language: Английский

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Screening seven‐electron boron‐centered radicals for dinitrogen activation

Journal of Computational Chemistry, Journal Year: 2023, Volume and Issue: 45(10), P. 648 - 654

Published: Dec. 11, 2023

Abstract The activation of dinitrogen is significant as nitrogen‐containing compounds play an important role in industries. However, the inert NN triple bond caused by its large HOMO‐LUMO gap (10.8 eV) and high dissociation energy (945 kJ mol −1 ) renders under mild conditions particularly challenging. Recent progress shows that a few main group species can mimic transition metal complexes to activate dinitrogen. Here, we demonstrate series seven‐electron (7e) boron‐centered radical be used N 2 via density functional theory calculations. It found radicals containing amine ligand perform best on thermodynamics activation. In addition, when electron‐donating groups are introduced at boron atom, these with low reaction barriers. Further analysis suggests electron transfer from atom π* orbitals essential for Our findings suggest great potential 7e field

Language: Английский

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Predicting Activation of Small Molecules Including Dinitrogen via a Carbene with a σ⁰π² Electronic Configuration

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(34), P. 15931 - 15940

Published: Aug. 9, 2024

Although the main group species in s and p blocks have begun to gain prominence field of dinitrogen (N2) activation recent years, reports carbene-mediated N2 remain particularly rare, especially for carbenes with a σ0π2 electronic configuration. Herein, we demonstrate examples initiated by carbene configuration consequent hydroboration reaction (with barrier as low 19.9 kcal/mol) via density functional theory calculations. Meanwhile, "push–pull" effect upon introduction hydroborenium complex facilitates generation thermodynamically kinetically more stable product. In addition, such can also activate series H–X (X = H, CH3, or Bpin) bonds through an oxidative addition process energies ranging from 6.0 18.0 kcal/mol. Our findings highlight importance small molecule activation, activation.

Language: Английский

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Predicting Dinitrogen Activation by Boron Radical Cations

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 3, 2025

Activation of dinitrogen (N2) under mild conditions has been a particularly challenging project for decades, owing to the highly strong N≡N triple bond. In recent years, main group species have emerged as prominent strategy in field activation, but reported examples remain rare compared with transition metal complexes. Herein, we performed comprehensive density functional theory (DFT) calculation N2 activation by boron radical cations. The calculations demonstrated that cations was favorable both kinetically and thermodynamically, high exothermicity (ΔG value -36.8 kcal/mol) low reaction barrier (7.3 kcal/mol), indicating feasibility conditions. Moreover, principal interacting spin orbitals (PISOs) intrinsic bond (IBOs) analyses revealed cation activated through two perpendicular interactions, including σ-type donation π-type backdonation. Additionally, further analysis implied backdonation is essential activation. Our findings offer an alternative approach metal-free highlighting significance chemistry

Language: Английский

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Exploring N2 activation using novel Lewis acid/base pairs: computational insight into frustrated Lewis pair reactivity†

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The activation of dinitrogen (N2) is a crucial step in synthesizing nitrogen-based compounds and remains significant challenge due to its strong triple bond. Currently, industrial N2 conversion relies on the Haber-Bosch process, highly energy-intensive method that utilizes transition metal-based catalysts. Frustrated Lewis pairs (FLPs) have emerged as promising alternative for without need metals. In this work, we employ density functional theory (DFT) investigate by metal-free acids (LAs) bases (LBs). Our study demonstrates LAs play role capturing determining thermodynamics activation, while LBs complementary reducing bond order molecule, thereby promoting activation. efficiency capture directly linked electroaccepting characteristics LAs. A principal component analysis (PCA) reveals key factors influencing power are degree pyramidalization orbital occupation at acidic site, well local electrophilicity index. LA-N2 interaction found be electrostatic with partially covalent character. Among 21 analyzed, triptycene-based systems exhibit highest stability forming complexes, highlighting their potential effective N2-capturing agents. However, largely intact, necessitating involvement LA-N2-LB complexes full "push-pull" mechanism. Six analyzed most Bonding indicates LB-N2 can regarded bond, which may explain main LB reduction order. Furthermore, significantly enhanced increasing nucleophilicity LB. all LA-LB pair combinations, only three defining frustrated (FLPs), moderate energies substantial distances. findings suggest FLPs composed tris-tert-butylphosphine represent candidates

Language: Английский

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Puppeteering the Reactivity of Frustrated Lewis Pairs toward CO2 via Coordination Dichotomy in Bridging Units

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The coordination dichotomy of the o -carborane cage has been investigated as a strategy to regulate frustration in frustrated Lewis pairs (FLPs).

Language: Английский

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Predicting σ⁰π² Carbene-Mediated Hydroboration and Bis-carbene Functionalization of Dinitrogen

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

Although the carbene-catalyzed N2 fixation process had been investigated by scientists for decades prior to borylene species, interest in carbene-mediated activation has drawn less attention than that of species past few years, especially unique σ0π2 carbenes. Herein, we demonstrate important role carbenes 1,1-hydroboration and bis-carbene functionalization using density functional theory calculations. Both being kinetically thermodynamically favorable, reaction barriers are as low 13.7 16.6 kcal/mol, respectively. Additionally, such a carbene can also achieve series X-H insertion reactions (X = H, CH3, Bpin, or SiH2Ph), with energies ranging from 8.2 15.3 kcal/mol. Our findings highlight strong potential electronic configuration its versatile transformations, providing valuable insights into main-group-element-mediated chemistry.

Language: Английский

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BN Analogue of Butadiyne: A Platform for Dinitrogen Release and Reduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(34), P. 18767 - 18772

Published: Aug. 15, 2023

Exploration of the metallomimetic chemistry main group elements is utmost importance from perspective both fundamental research and potential applications. Here, we report synthesis, bonding analysis, reactivities an isolable diiminoborane, Mes*B≡N─N≡BMes* (Mes* = 2,4,6-tri-tert-butylphenyl) (1), a BN analogue butadiyne. This species characterized by conjugated B≡N─N≡B moiety, structural feature that enables controlled release N2 when it exposed to organic nitriles. Furthermore, unit in 1 could be reduced ammonium salt via cleavage triple bond. Our work shows rare example unsaturated system, serving as platform for reduction N2. discovery opens new pathways holds substantial influence on future design functional species.

Language: Английский

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Predicting dinitrogen activation by borenium and borinium cations

Physical Chemistry Chemical Physics, Journal Year: 2022, Volume and Issue: 24(23), P. 14651 - 14657

Published: Jan. 1, 2022

The activation of thermodynamically stable and kinetically inert dinitrogen (N2) has been a great challenge due to the significant strength triple bond. Recently, in an experimental study on N2 by boron species, highly reactive two-coordinated borylene broke through limitations traditional strategies metal species. Still, studies metal-free remain underdeveloped. Here, we systematically investigate frustrated Lewis pair (FLP) combining carbene borenium (or borinium) cations screen potential candidates for via density functional theory calculations. As result, found that two FLPs (closed form FLP, open are able activate favorable manner, with low energy barrier 9.6 7.3 kcal mol-1, respectively. Furthermore, aromaticity was play important role stabilization products, supported nucleus-independent chemical shift (NICS), anisotropy current-induced (ACID) electron delocalized bonds (EDDB) analysis. Our findings provide alternative approach activation, highlighting importance FLP chemistry activation.

Language: Английский

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