Manipulation of Solvent Donor Effects to Overcome the Calcium Schlenk Equilibrium DOI
Kaitlyn M. Birkhoff, I-Hsin Lin,

Sam Yruegas

и другие.

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 16, 2025

Synthetic access toward well-defined, monomeric s-block metal complexes is mired with chemical challenges, primarily attributed to the formation of homoleptic promoted by Schlenk equilibrium. Ligand redistribution significantly pronounced for heavier metals, such as calcium, which form bischelate readily through traditional synthetic routes transmetalation, amination, and ligand exchange. Mechanistic investigation each these phenoxyimine (ONN) ligands was explored ascertain fundamental parameters promote formation. Donor effects from coordinated solvent proved be deleterious, in an effort circumvent bischelation, a new calcium bisamide, {Ca[N(SiMe3)2]2(diox)2}∞, synthesized characterized coordination polymer unique square planar geometry, rarely seen group 2 complexes. Amination {Ca[N(SiMe3)2]2(diox)2}∞ found shift equilibrium favor heteroleptic species, allowing characterization calcium-amido complexes: [ONN1Ca-N(SiMe3)2]2(diox) [ONN3Ca-N(SiMe3)2(diox)]∞. Subsequent studies showed that exchange isolated dioxane THF notably shortened stability complex solution. Although steric have previously been regarded key stabilization complexes, it equally important consider donor ability achieve longer-lived heavy

Язык: Английский

Facile synthesis of Sn-doped MOF-5 catalysts for efficient photocatalytic nitrogen fixation DOI
Lixia Li,

Xiangyi Lv,

Liujuan Jin

и другие.

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 344, С. 123586 - 123586

Опубликована: Дек. 18, 2023

Язык: Английский

Процитировано

46

Low oxidation state and hydrido group 2 complexes: synthesis and applications in the activation of gaseous substrates DOI
Matthew J. Evans, Cameron Jones

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 5054 - 5082

Опубликована: Янв. 1, 2024

This review summarises advances in the chemistry of low-oxidation state and hydrido group 2 metal complexes, focussing on their use for reductive activation feed-stock gaseous small molecules, subsequent transformation into value added products.

Язык: Английский

Процитировано

20

P‐Block Metal‐Based Electrocatalysts for Nitrogen Reduction to Ammonia: A Minireview DOI
Shaoquan Li, Yingnan Wang, Yue Du

и другие.

Small, Год журнала: 2023, Номер 19(16)

Опубликована: Янв. 6, 2023

Electrochemical nitrogen reduction reaction (NRR) to ammonia (NH3 ) using renewable electricity provides a promising approach towards carbon neutral. What's more, it has been regarded as the most alternative traditional Haber-Bosch route in current context of developing sustainable technologies. The development class highly efficient electrocatalysts with high selectivity and stability is key electrochemical NRR. Among them, P-block metal-based have significant application potential NRR for which possessing strong interaction N 2p orbitals. Thus, offers good NH3 . density state (DOS) near Fermi level concentrated catalysts, indicating ability metal active sites N2 adsorption activation by donating p electrons. In this work, we systematically review recent progress effect on activity, are discussed. Specifically, catalyst design, nature some strategies boosting performance, mechanism, impact operating conditions unveiled. Finally, challenges outlooks proposed.

Язык: Английский

Процитировано

35

Coordination and Activation of N2 at Low‐Valent Magnesium using a Heterobimetallic Approach: Synthesis and Reactivity of a Masked Dimagnesium Diradical** DOI Creative Commons
Rahul Mondal, Matthew J. Evans, Thayalan Rajeshkumar

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(37)

Опубликована: Июль 21, 2023

Abstract The activation of dinitrogen (N 2 ) by transition metals is central to the highly energy intensive, heterogeneous Haber–Bosch process. Considerable progress has been made towards more sustainable homogeneous activations N with d‐ and f‐block metals, though little success had main group metals. Here we report that reduction a bulky magnesium(II) amide [( TCHP NON)Mg] ( NON=4,5‐bis(2,4,6‐tricyclohexylanilido)‐2,7‐diethyl‐9,9‐dimethyl‐xanthene) 5 % w/w K/KI yields magnesium‐N complex [{K( NON)Mg} (μ‐N )]. DFT calculations experimental data show unit in reduced 2− dianion, via transient anionic magnesium(I) radical. compound readily reductively activates CO, H C 4 , reactions which it acts as masked dimagnesium(I) diradical.

Язык: Английский

Процитировано

28

Dinitrogen Activation and Addition to Unsaturated C−E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes DOI
Qingde Zhuo, Xiaoxi Zhou, Takanori Shima

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Фев. 6, 2023

Abstract Dinitrogen (N 2 ) activation and functionalization is of fundamental interest practical importance. This review focuses on N addition to unsaturated substrates, including carbon monoxide, dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, allenes, mediated by transition metal complexes, which afforded a variety N−C bond formation products. Emphases are placed the reaction modes mechanisms. We hope that this work would stimulate further explorations in challenging field.

Язык: Английский

Процитировано

26

Flatland materials for photochemical and electrochemical nitrogen fixation applications: from lab-door experiments to large-scale applicability DOI
Syed Asim Ali,

Iqra Sadiq,

Tokeer Ahmad

и другие.

Sustainable Energy & Fuels, Год журнала: 2024, Номер 8(16), С. 3476 - 3495

Опубликована: Янв. 1, 2024

Flatland materials were meticulously surveyed to explore their functionality in photochemical and electrochemical nitrogen reduction reaction applications. New insights are presented for pilot-scale NRR operations via 2D materials.

Язык: Английский

Процитировано

14

Selective nitrogen fixation via Janus C-N coupling in co-electrolysis DOI
Xiaoran Zhang, Xiaorong Zhu,

Shuowen Bo

и другие.

Chem, Год журнала: 2024, Номер 10(5), С. 1516 - 1527

Опубликована: Фев. 21, 2024

Язык: Английский

Процитировано

12

Synergistic effects of CQDs and oxygen vacancies on CeO2 photocatalyst for efficient photocatalytic nitrogen fixation DOI

Mingxiao Cheng,

Wanjun Li, Ziyuan Wu

и другие.

Separation and Purification Technology, Год журнала: 2024, Номер 354, С. 129299 - 129299

Опубликована: Авг. 23, 2024

Язык: Английский

Процитировано

11

Construction of N−E bonds via Lewis acid-promoted functionalization of chromium-dinitrogen complexes DOI Creative Commons
Zhu‐Bao Yin, Gao‐Xiang Wang, Xuechao Yan

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 15, 2025

Язык: Английский

Процитировано

2

Tailored Dynamic Seesaw Configuration of Heterojunctions to Enhance Piezo-Photocatalytic Overall Nitrogen Fixation DOI

Qin Luo,

Xiaoxu Deng, Tianxiang Zhao

и другие.

Nano Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 3, 2025

Relay overall nitrogen fixation presents an intriguing approach to the simultaneous production of nitric acid and ammonia. However, it remains a significant challenge due manipulating dual active sites on both temporal spatial mesoscopic scales. In this study, we propose bionic seesaw Bi4O5Cl2-Bi4O5Br2 heterojunction, which establishes one-way reaction channel through entanglement effect, challenging inherent idea synchronous in heterojunction. Notably, adaptive interface functions as fulcrum by incorporating tensile Bi-Cl bonds compressive Bi-Br while also inducing localized surface lattice distortion Bi-O sequentially activate sites. Therefore, unsaturated dynamic properties trigger structure enhance charge exchange molecular polarization N2 during reduction, thereby creating hydroxy-rich environment for ammonia oxidation process. Our work offers novel site control perspective clarifies processes.

Язык: Английский

Процитировано

2