Cycloadditions of Diazoalkenes with P₄ and tBuCP: Access to Diazaphospholes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(38)

Published: July 1, 2024

Diazoalkenes readily react with tert-butylphosphaalkyne (tBuCP) and white phosphorus (P

Language: Английский

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A Lead(II) Substituted Triplet Carbene

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29630 - 29636

Published: Oct. 18, 2024

Reaction of the pincer-type ligand L

Language: Английский

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Phosphine/Sulfoxide-Carbone, a Ligand with a Flexible Bonding Mode for Early to Late Transition Metals

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

Published: Jan. 1, 2025

In recent years, carbones have emerged as a new exciting class of carbon-based ligands. We report here series organometallic complexes demonstrating the versatility in coordination mode phosphine/sulfoxide carbone 1. Indeed, 1 is able to chelate both early and late transition metals, mono- or bidentate fashion depending on oxyphilic character metal center thanks presence sulfoxide moiety. All been fully characterized by X-ray diffraction analysis NMR spectroscopy (except hafnium complex because its extreme insolubility). It noteworthy that silver(I) zirconium(IV) are efficient transmetalating reagents toward copper(I) complexes.

Language: Английский

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Stable crystalline keteniminyl anions

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102444 - 102444

Published: Feb. 1, 2025

Language: Английский

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Exploring Singlet Carbyne Anions and Related Low-Valent Carbon Species Utilizing a Cyclic Phosphino Substituent

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

ConspectusThe advancement of synthetic methodologies is fundamentally driven by a deeper understanding the structure–reactivity relationships reactive key intermediates. Carbyne anions are compounds featuring monovalent anionic carbon possessing four nonbonding valence electrons, which were historically confined to theoretical constructs or observed solely within environment gas-phase studies. These species possess potential for applications across diverse domains chemistry and ancillary fields. This Account details our focused efforts isolate singlet carbyne explores isolation range related low-valent species. Our achievements include synthesis characterization, under normal laboratory conditions, gold-substituted free carbenes, copper anion complexes, ketenyl anions, keteniminyl stannyne. have been accomplished using bulky cyclic phosphino substituent, effectively stabilizes these species.Our journey commenced with phosphinocarbenes, characterized robust carbon–gold covalent single bond, progressed complexes carbon–copper ionic bond. was realized through synergistic combination group closed-shell electron-rich late transition metal. The robustness bond contrasts markedly susceptibility imparts behavior characteristic phosphinocarbyne coordination sphere copper, thereby enabling unique transfer reactions. tri-active ambiphilic nature in enables formation three chemical bonds at center one-pot Subsequent investigations unveiled ligand exchange reactions site, leading generation stable crystalline anions. emerge as potent synthons capable producing array derivatives. In addition, we isolated phosphinostannyne, rare carbon–tin multiple two adjacent centers. Collectively, demonstrated remarkable propensity engaging spectrum reactions, underscoring their versatility confirming utility synthesizing uncharted, main species.The insights derived from research contribute broader may provide platform future innovations chemistry, catalytic processes, novel materials. As continue explore develop this area study, hope that might follow footsteps potentially finding various fields future.

Language: Английский

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The lithium effect in ketenyl anion chemistry

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(70), P. 9372 - 9375

Published: Jan. 1, 2024

Ketenyl lithium compounds of type [RC(Li)CO] (with R = Ph

Language: Английский

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An Azide-Free Synthesis of Metallodiazomethanes Using Nitrous Oxide

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(35), P. 24602 - 24608

Published: Aug. 20, 2024

Diazo compounds are valuable reagents in synthesis but usually require the use of potentially explosive or toxic starting materials. Here, we report and isolation alkali metal diazomethanides by reaction metalated ylides with nitrous oxide, resulting a formal exchange phosphine ligand dinitrogen. The proceeds through Wittig-like mechanism via [3 + 2] cycloaddition N2O across ylide bond release oxide. diazomethanes exhibit an increased thermal stability due to stronger binding N2 compared neutral diazomethanes. This is reflected short C–N distances red-shifted N–N vibrations enables versatile applications such as for preparation transition diazomethanide complexes 1,2,3-triazoles from nitriles, diazoacetates carbon dioxide, alkynes aldehydes.

Language: Английский

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(Imidazol-2-ylidene)→S Coordination Interaction and its Modulation Upon S-Oxidation

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

NHCs donate electron density to a sulfur centre in the NHC → S–R + species. This dative bond becomes weaker upon S -oxidation, as observed from experimental and quantum chemical analyses.

Language: Английский

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Crystalline Keteniminyl Anions

Research Square (Research Square), Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 1, 2024

The synthesis, characterization, and reactivity of keteniminyl anions [R¹C = C NR²]⁻, a hitherto uncharted functional group, are the primary focus this study. Our comprehensive analyses, including NMR spectroscopy, X-ray crystallography, density theory calculations, have illuminated distinct electronic characteristics these anions. They characterized by their nucleophilic/basic anionic carbon π electrons, which extensively delocalized along PCCN chain. These undergo range facile reactions, such as protonation, alkylation, silylation, metalation at site, leading to various ketenimine derivatives. also participate in hydroamination yielding amino enamide groups. Additionally, phosphino substituent acts previously underappreciated weak π-electron acceptor when phosphorus atom is pyramidalized state, thereby facilitating stabilization electron-rich carbon. isolation thiophosphino not only represents significant synthetic achievement but heralds potential for future novel species featuring substituents.

Language: Английский

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Cycloadditionen von Diazoalkenen mit P₄ und tBuCP: Ein Zugang zu Diazaphospholen

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(38)

Published: July 1, 2024

Abstract Reaktionen von Diazoalkenen mit tert ‐Butylphosphaalkin ( t BuCP) und weißem Phosphor (P 4 ) führen zu neuen Phosphorheterocyclen, 3 H ‐1,2,4‐Diazamonophospholen 1,2,3,4‐Diazadiphospholen. Die erhaltenen Verbindungen sind seltene Beispiele für neutrale Heterophosphole. Der Bildungsmechanismus der formalen (3+2)‐Cycloadditionsprodukte wurde quantenchemisch berechnet die elektronischen Strukturen analysiert. Phosphole bilden strukturell vielfältige Koordinationsverbindungen Übergangsmetallen Hauptgruppenelementen. Angesichts wachsenden Anzahl stabiler Diazoalkene bietet diese Arbeit einen unmittelbaren Zugang neutralen Aza(di‐)phospholen als neue Ligandenklasse.

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