Isolation and characterization of a triplet nitrene

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 38 - 43

Published: Nov. 19, 2024

Language: Английский

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Transient Triplet Metallopnictinidenes M–Pn (M = Pd^II, Pt^II; Pn = P, As, Sb): Characterization and Dimerization

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity this important class transient intermediates has attributed their electronic structures, particularly the accessibility triplet vs singlet states. In contrast, structure trends along heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report synthesis series metallodipnictenes, {M–Pn═Pn–M} (M PdII, PtII; P, As, Sb, Bi) characterization metallopnictinidene intermediates, {M–Pn} for Sb. Structural, spectroscopic, computational analysis revealed spin ground states metallopnictinidenes with characteristic series. comparison nitrene, pnictinidenes exhibit lower-lying state SOMOs excited states, thus suggesting increased electrophilic reactivity. Furthermore, splitting magnetic microstates is beyond phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Language: Английский

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A singly bonded gallanediyl with redox-active and redox-inert reactivity

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

Language: Английский

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Copper and Silver Trispyrazolylborate-Phosphinoazide Complexes: Synthesis, Characterization, and Nitrene Generation

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: 64(1), P. 151 - 157

Published: Jan. 2, 2025

Phosphinoazide complexes of the composition TpBr3M-L (M = Cu, Ag, and L 2-azido-1,3-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaphosphole) have been synthesized structurally characterized. Their thermal decomposition led to cyclodiphosphazenes as a result metal-mediated coupling two nitrene units in process that takes place both stoichiometric catalytic manner. Experimental data allowed proposing mechanistic pathway for this new transformation.

Language: Английский

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Bottleable triplet nitrenes

Nature Chemistry, Journal Year: 2025, Volume and Issue: 17(1), P. 6 - 7

Published: Jan. 1, 2025

Language: Английский

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Exploring Stibanyl Ligand for Accessing Arsinidene and Arsaketene Adducts, and Phosphaketene

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

Published: Jan. 9, 2025

The salt metathesis reaction involving a diamine-based antimony chloride precursor with sodium arsaethynolate in the presence of PMe3 leads to formation stibanyl-functionalized PMe3-arsinidene (2). Detailed analyses through single-crystal X-ray diffraction and density functional theory 2 confirm covalent Sb-As bonds reveal its polarized nature multiple-bond character. In contrast complex 2, substituting xylyl isocyanide or 1,3-diisopropyl-4,5-dimethyl-imidazolin-2-ylidene (IiPr) produces an isocyanide-arsinidene adduct (3) IiPr-arsaketene (4), respectively. Furthermore, related reactions 1 phosphaethynolate yield both stibanyl-phosphaketene (5) IiPr-phosphaketene (6).

Language: Английский

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Synthesis and magnetic property of a telluryl radical

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102392 - 102392

Published: Jan. 1, 2025

Language: Английский

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Trendbericht Anorganische Chemie 2024: Hauptgruppen‐ und Molekülchemie

Nachrichten aus der Chemie, Journal Year: 2025, Volume and Issue: 73(2), P. 46 - 55

Published: Jan. 31, 2025

Abstract Das erste heterobimetallische Dimetallocen; mit sterisch anspruchsvollen Liganden lassen sich einfach‐koordinierte Hauptgruppenverbindungen der Gruppen 13 bis 15 herstellen; neue Diazoverbindungen erlauben es, B‐R‐Einheiten und Kohlenstoffatome zu übertragen.

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Photogeneration and Visualization of a Surface‐Stabilized Dinitrene

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 6, 2025

Nitrenes are known as key intermediates in various chemical reactions. Nitrene transfer reactions particularly effective for synthesizing nitrogen-containing compounds, where metal catalysts play a crucial role controlling nitrene reactivity and selectivity. In this study, we demonstrate the formation of stable surface-supported dinitrene on Au(111) through UV irradiation its diazide precursor, characterized by scanning probe techniques. The photoreaction mechanism is elucidated with wavelength-dependent experiments time-dependent density functional theory calculations. Our findings present first real-space visualization adsorbed surface, highlighting potential catalysis surface functionalization.

Language: Английский

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A Crystalline Nitrogen Chain Radical Anion

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Long chain nitrogen ions and radicals ([N_n]^x+ / [N_n]^x–, n > 3) are naturally occurring under the intense radiative conditions of Earth’s ionosphere, those other planetary bodies. However, strong thermodynamic driving force to lose N₂ renders these types molecules extremely reactive ambient such that they can typically be studied only extreme conditions, for example at ultrahigh pressures (10 >200 GPa). We now report isolation a molecule featuring metal-unsupported {N₄}^•– unit which demonstrates remarkable multi-week long persistence in solid-state. Spectroscopic, crystallographic computational studies provide insight into bonding across chain. Reactivity reveal cleave N1 N3 fragments, act as source nitrene radical anion, an observation could storable group transfer reagents.

Language: Английский

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