Coordination-induced polymerization of P═C bonds leads to regular (P─C)
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            polycarbophosphanes

Mei, Yanbo; Gamboa‐Carballo, Juan José; Bao, Yinyin; Wu, Na; Corre, Grégoire Le

doi:10.1126/sciadv.abf4272

Cited by 6 publications

(1 citation statement)

References 41 publications

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“… 27 Very recently, this methodology even enabled the construction of “depolymerizable” coordination polymers. 28 Although several heterocycles can be obtained using the [PCO] − anion, these reactions typically proceed rather in a stepwise manner (via consecutive nucleophilic attacks) instead of following a concerted mechanism [such as in more conventional pericyclic reactions, e.g., Diels–Alder (DA) reactions]. 14 , 20 , 26 , 29 …”

Section: Introductionmentioning

confidence: 99%

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions

Benkő

2022

Inorg. Chem.

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While Diels–Alder (DA) reactions involving neutral or cationic dienophiles are well-known, the characteristics of the analogous reactions with anionic dienophiles are practically unexplored. Herein we present the first comparative computational investigations on the characteristics of DA cycloadditions with anionic dienophiles on the basis of the reactions of [ECX] − anions (E = P, As; X = O, S, Se) with 2 H -pyran-2-one. All of these reactions were found to be both kinetically and thermodynamically feasible, enabling synthetic access toward 2-phosphaphenolate and arsaphenolate derivatives in the future. This study also reveals that the [ECO] − anions show clear regioselectivity, while for [ECS] − and [ECSe] − anions, the two possible reaction channels have very similar energetics. Additionally, the activation barriers for the [ECO] − anions are lower than those of the heavier analogues. The observed differences can be traced back to the starkly differing nucleophilic character of the pnictogen center in the anions, leading to a barrier-lowering effect in the case of the [ECO] − anions. Furthermore, analysis of the geometries and electron distributions of the corresponding transition states revealed structure–property relationships, and thus a direct comparison of the cycloaddition reactivity of these anions was achieved. Along one of the two pathways, a good correlation was found between the activation barriers and suitable nucleophilicity descriptors (nucleophilic Parr function and global nucleophilicity). Additionally, the tendency of the reaction energies can be explained by the changing aromaticity of the products.

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Section: Introductionmentioning

confidence: 99%

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions

Benkő

2022

Inorg. Chem.

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Lifecycle Management for Sustainable Plastics: Recent Progress from Synthesis, Processing to Upcycling

Yang,

Li,

Nie

et al. 2024

Advanced Materials

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Plastics, renowned for their outstanding properties and extensive applications, assume an indispensable and irreplaceable role in modern society. However, the ubiquitous consumption of plastic items has led to a growing accumulation of plastic waste. Unreasonable practices in the production, utilization, and recycling of plastics have led to substantial energy resource depletion and environmental pollution. Herein, the state‐of‐the‐art advancements in the lifecycle management of plastics are timely reviewed. Unlike typical reviews focused on plastic recycling, this work presents an in‐depth analysis of the entire lifecycle of plastics, covering the whole process from synthesis, processing, to ultimate disposal. The primary emphasis lies on selecting judicious strategies and methodologies at each lifecycle stage to mitigate the adverse environmental impact of waste plastics. Specifically, the article delineates the rationale, methods, and advancements realized in various lifecycle stages through both physical and chemical recycling pathways. The focal point is the attainment of optimal recycling rates for waste plastics, thereby alleviating the ecological burden of plastic pollution. By scrutinizing the entire lifecycle of plastics, the article aims to furnish comprehensive solutions for reducing plastic pollution and fostering sustainability across all facets of plastic production, utilization, and disposal.

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Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

Walsgrove,

Percival,

Gates

2023

Chemistry A European J

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Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (μSR) is a highly sensitive method that can detect radical species at 106 spins (cf. EPR: 1012 spins, NMR: 1018 spins). Herein, we employ μSR to detect the radical‐addition products from three 1‐phosphabutadiene monomers, P‐analogues of isoprene. We show that muonium (Mu), a “light” H‐atom surrogate, adds predominantly at the C4 position of the P1=C2−C3=C4 moiety to give unprecedented 1‐phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT‐calculations. A minor radical product is also detected that is tentatively assigned to an PC3‐heterocyclic free radical. On the basis of DFT‐predictions, we speculate that its formation may involve initial addition of Mu+ at the C3 position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1‐phosphabutadienes, which have previously been polymerized using anionic initiation.

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Coordination-induced polymerization of P═C bonds leads to regular (P─C) _n polycarbophosphanes

Cited by 6 publications

References 41 publications

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions

Lifecycle Management for Sustainable Plastics: Recent Progress from Synthesis, Processing to Upcycling

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

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Coordination-induced polymerization of P═C bonds leads to regular (P─C) n polycarbophosphanes

Cited by 6 publications

References 41 publications

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]− (E = P, As; X = O, S, Se) Anions

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]− (E = P, As; X = O, S, Se) Anions

Lifecycle Management for Sustainable Plastics: Recent Progress from Synthesis, Processing to Upcycling

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

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Product

Resources

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Coordination-induced polymerization of P═C bonds leads to regular (P─C) _n polycarbophosphanes

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions

Understanding the Mechanism of Diels–Alder Reactions with Anionic Dienophiles: A Systematic Comparison of [ECX]⁻ (E = P, As; X = O, S, Se) Anions