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

A. Jagadeesh,

Prashant Galav

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15851 - 15863

Published: Oct. 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.

Language: Английский

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

et al.

Small, Journal Year: 2025, Volume and Issue: unknown

Published: April 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.

Language: Английский

Citations

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

A. Jagadeesh,

Prashant Galav

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(21), P. 15851 - 15863

Published: Oct. 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.

Language: Английский

Citations

1