Moderation of the Electronic Structure of Phosphamides to Execute the Catalytic Appel Reaction Bypassing Phosphine DOI
Nidhi Kumari,

A. Jagadeesh,

Prashant Galav

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 15851 - 15863

Опубликована: Окт. 19, 2024

A set of structurally analogous, albeit electronically distinct, phosphamides (1aa-10aa) is prepared, and the effect electronic amendment due to p-substitution has been tested for conversion alcohols halides via Appel reaction. The −OMe-substituted diphosphamide (8aa) remains most active, providing ∼96% with a TON 11 in moderate reaction conditions large substrate scope. Halide formation follows pseudo-first-order rate constant (kobs) 7.13 × 10–5 s–1. Temp-dependent kinetics Eyring analyses reveal activation parameters ΔH‡ 28.95 (±1.6) kcal mol–1, ΔS‡ −70.02 (±0.4) cal K–1 ΔG‡298 49.81 (±1.2) mol–1. deuterium labeling study highlights O–H dissociation alcohol as rate-determining step, while Hammett analysis p-substituted benzyl indicates positive charge accumulation at phosphorus center during HOMO–LUMO energy NPA show that p–OMe substitutions 8aa make "P═O" bond more ionic corresponding aminophosphine nucleophilic, which are favorable In situ detection salt, [R3PX]CX3 alkoxy phosphonium cation [R3POR]X, validates pathway mediated by phosphamides.

Язык: Английский

Poly‐Phosphamide Catalyzed Visible‐Light‐Driven CH4 and Dark‐Phase‐Mediated Cyclic Carbonate Productions Utilizing CO2 DOI
Nidhi Kumari, Kaushik Das, Monika Chaudhary

и другие.

Small, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Abstract A poly‐phosphamide (POP) with a band gap of 2.8 eV is used for the photochemical conversion CO 2 into CH 4 and chemical organo‐epoxides cyclic carbonates. The Tauc plot Mott Schottky analyses indicate conduction potential at −1.49 V (vs NHE), much more negative than multi‐electron reduction lifetime photo‐excited electron found ns. On photoirradiation 420 nm light, POP in presence triethanolamine or ascorbic acid can selectively convert (≈99%) yield 4.6 mmol g −1 . visible‐light irradiation, drop charge‐transfer resistance (R ct ) an enhancement cathodic current further confirm photon‐harvesting efficiency POP. In situ, FTIR study identifies adsorption to possible reaction intermediate, like *‐CO, *‐CH OH. also behaves as catalyst carbonates under solvent‐free conditions 98% yield. After light‐phase dark‐phase reactions, be successfully recycled least five times without structural degradation. Herein, acts bi‐functional, recyclable polymeric organic material essential feedstocks mild conditions.

Язык: Английский

Процитировано

0
Moderation of the Electronic Structure of Phosphamides to Execute the Catalytic Appel Reaction Bypassing Phosphine DOI
Nidhi Kumari,

A. Jagadeesh,

Prashant Galav

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 15851 - 15863

Опубликована: Окт. 19, 2024

A set of structurally analogous, albeit electronically distinct, phosphamides (1aa-10aa) is prepared, and the effect electronic amendment due to p-substitution has been tested for conversion alcohols halides via Appel reaction. The −OMe-substituted diphosphamide (8aa) remains most active, providing ∼96% with a TON 11 in moderate reaction conditions large substrate scope. Halide formation follows pseudo-first-order rate constant (kobs) 7.13 × 10–5 s–1. Temp-dependent kinetics Eyring analyses reveal activation parameters ΔH‡ 28.95 (±1.6) kcal mol–1, ΔS‡ −70.02 (±0.4) cal K–1 ΔG‡298 49.81 (±1.2) mol–1. deuterium labeling study highlights O–H dissociation alcohol as rate-determining step, while Hammett analysis p-substituted benzyl indicates positive charge accumulation at phosphorus center during HOMO–LUMO energy NPA show that p–OMe substitutions 8aa make "P═O" bond more ionic corresponding aminophosphine nucleophilic, which are favorable In situ detection salt, [R3PX]CX3 alkoxy phosphonium cation [R3POR]X, validates pathway mediated by phosphamides.

Язык: Английский

Процитировано

1