Microwave activation of the reaction of red phosphorus with alkanethiolate anions

Трофимов, Б. А.; Гусарова, Н. К.; Verkhoturova, S. I.; Mikhailenko, V. L.; Kazantseva, T. I.; Arbuzova, S. N.

doi:10.1134/s1070363209110309

Cited by 9 publications

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References 4 publications

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“…A few reports described the use of thiolates for activation of P red or P white in the presence of H 2 O to produce thiophosphites or thiophosphates. − Likewise, we conducted reactions with various alkyl thiolates (Table ) to evaluate their potential for activating P red under reaction conditions similar to those used with alkoxides. A mixture of P red and thiolate was heated in refluxing THF/DME (1:1 v/v).…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides

Dragulescu‐Andrasi

Miller

et al. 2020

Inorg. Chem.

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Reactions between red phosphorus (P red ) and potassium ethoxide in various organic solvents under reflux convert this rather inert form of the element to soluble polyphosphides. The activation is hypothesized to proceed via a nucleophilic attack by ethoxide on the polymeric structure of P red , leading to disproportionation of the latter, as judged from observation of P(OEt) 3 in the reaction products. A range of solvents has been probed, revealing that different polyphosphide anions (P 7 3− , P 16 2− , P 213− , and P 5 − ) can be stabilized depending on the combination of the boiling point and dielectric constant (polarity) of the solvent. The effectiveness of activation also depends on the nature of nucleophile, with the rate of reaction between P red and KOR increasing in the order t-Bu < n-Hex < Et < Me, which is in agreement with the increasing order of nucleophilic strength. Thiolates and amides were also examined as potential activators, but the reaction with these nucleophiles were substantially slower; nonetheless, all reactions between P red and NaSR yielded exclusively P 16 2− as a soluble polyphosphide product.

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Section: Resultsmentioning

confidence: 99%

Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides

Dragulescu‐Andrasi

Miller

et al. 2020

Inorg. Chem.

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“…The dissociation of P 4 to P 2 molecules, which later recombine to photochemically produce RP upon polymerization is often associated with the participation of electromagnetic radiation in which UV radiation has been acclaimed to accelerate the conversion of white P 4 to RP allotropes. , The activation of P 4 molecules by electromagnetic radiation is depicted in Figure , Path a . Light activation for the transformation of white P 4 into the red variety was initiated and described in two historical reports prepared by Pedler and Rathenau who opened up new possibilities to produce phosphorus–carbon (P–C) bond by utilizing ionizing radiation such as UV energy source and electromagnetic radiation in the X-ray or γ range to activate the P 4 molecule. − The primary mechanism proposed for the conversion of WP to the red form involved symmetrically cleaving the P 4 molecule before recombining the resulting P 2 unit to configure the final RP polymer . In contrast to the electromagnetic radiation synthesis method, the transformation of white P 4 to RP allotropes by high temperature heating at 1000 to 1500 °C under inert conditions released a product gas consisting of equilibrium P 4 and P 2 molecules (Figure , Path f), the P 4 molecule in the solution then photolyzed at ambient conditions to form P 2 molecules which underwent polymerization subsequently to generate RP. − …”

Section: Synthesis Of Red Phosphorus Allotropesmentioning

confidence: 99%

Red Phosphorus: An Up-and-Coming Photocatalyst on the Horizon for Sustainable Energy Development and Environmental Remediation

Fung

Tan

et al. 2021

Chem. Rev.

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Photocatalysis is a perennial solution that promises to resolve deep-rooted challenges related to environmental pollution and energy deficit through harvesting the inexhaustible and renewable solar energy. To date, a cornucopia of photocatalytic materials has been investigated with the research wave presently steered by the development of novel, affordable, and effective metal-free semiconductors with fascinating physicochemical and semiconducting characteristics. Coincidentally, the recently emerged red phosphorus (RP) semiconductor finds itself fitting perfectly into this category ascribed to its earth abundant, low-cost, and metal-free nature. More notably, the renowned red allotrope of the phosphorus family is spectacularly bestowed with strengthened optical absorption features, propitious electronic band configuration, and ease of functionalization and modification as well as high stability. Comprehensively detailing RP’s roles and implications in photocatalysis, this review article will first include information on different RP allotropes and their chemical structures, followed by the meticulous scrutiny of their physicochemical and semiconducting properties such as electronic band structure, optical absorption features, and charge carrier dynamics. Besides that, state-of-the-art synthesis strategies for developing various RP allotropes and RP-based photocatalytic systems will also be outlined. In addition, modification or functionalization of RP with other semiconductors for promoting effective photocatalytic applications will be discussed to assess its versatility and feasibility as a high-performing photocatalytic system. Lastly, the challenges facing RP photocatalysts and future research directions will be included to propel the feasible development of RP-based systems with considerably augmented photocatalytic efficiency. This review article aspires to facilitate the rational development of multifunctional RP-based photocatalytic systems by widening the cognizance of rational engineering as well as to fine-tune the electronic, optical, and charge carrier properties of RP.

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“…The essence of these reactions consists of the cleavage of the white‐phosphorus P–P bond in superbase media and their simultaneous capture with appropriate electrophiles to form phosphorus derivatives containing a C–P bond (Scheme ) 16e. It is important to point out that the reaction was also possible with two active varieties of red phosphorus (P n ), which were prepared by polymerization of white phosphorus (P 4 ) in the presence of carbon, graphite and organophosphorus molecules in benzene at room temperature under γ radiation ( 60 Co) and certain external treatment (X‐ray irradiation and mechanochemical treatment) 15c,16b,16c,16d. The two obtained new varieties of red phosphorus contain P–P, P–C and P–O–C bonds and more interestingly the presence of P–P–R defects, in which R is a graphite fragment or benzene, respectively, which were identified by IR and X‐ray electron spectroscopy.…”

Section: Photoactivation Of P4mentioning

confidence: 99%

Elemental Phosphorus and Electromagnetic Radiation

2014

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White phosphorus (P 4 ) is a small molecule that is mainly used as a starting material for the large-scale synthesis of most of the suitable phosphorus derivatives. The process starts with the direct reaction of P 4 with Cl 2 , and the resulting phosphorus chloride is further treated with the adequate organic substrate. This industrial process is very primitive, and for economic and environmental reasons the first oxidation step should be avoided. The observation that the conversion of white P 4 to the red allotrope is accelerated by ultraviolet light showed that the P 4 molecule is able to be activated by elec-[a] Área www.eurjic.org MICROREVIEW (Scheme 2, path b), which is actually widely studied, [4][5][6] but the straightforward addition of a nucleophile to the P 4 framework has also been investigated. [4c,4d,7] Scheme 2. (a) Method used to functionalize white phosphorus. (b) Functionalization of P 4 mediated by its coordination to a transition metal.Very meaningful reviews have classified and discussed the most significant reactivity of P 4 and the resulting products. [4,5a-5f] Nevertheless, to the best of our knowledge, until now there has been no review that summarizes the connection found between P 4 and electromagnetic radiation. With the purpose of filling this gap, herein we present the most significant known processes that involve electromagnetic radiation and the P 4 molecule. Photochemical Properties of White Phosphorus: White Phosphorus GlowThe phosphorus glow was first observed when phosphorus was discovered. Nevertheless, until the middle of the Manuel Serrano-Ruiz completed his B.Sc. degree at the San Marcos University (Peru) and he received his Ph.D. at the University of Almería (July 2010) under the supervision of Prof. A . Romerosa. His research interest is characterized by its multidisciplinary nature, including synthetic homogeneous catalysis in water, structural and characterization studies, and by a large network of collaborations. He is Collaborator Professor at the Departament of Chemistry and Physics of the University of Almeria in the department of Inorganic Chemistry (2011), coauthor of more than twenty scientific papers in peer-reviewed journals and he has been supervisor of a Ph.D. student with "Doctor Europeans Mention" (December 2012) on the synthesis and study of catalytic and photochemical properties of new water-soluble ruthenium complexes. Almeria. His research interests cover homogeneous catalysis in water and organometallics, phosphorus, photo-and bioinorganic chemistry. He has authored 110 international refereed papers, made more than 180 presentations at national and international meetings and supervised more than 14 Ph.D. students. The theses of most of them received "Doctor Europeans Mention". Pablo Lorenzo-Luis completed his B.Sc. Degree at the La Laguna University (ULL) and he received his Ph.D. from the same University (July 1998) under the supervision of Full Professor P. Gili. Soon after, he moved to ISSECC-CNR-Florence, Italy, with Dr. S. Midollini where he wo...

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Microwave activation of the reaction of red phosphorus with alkanethiolate anions

Cited by 9 publications

References 4 publications

Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides

Nucleophilic Activation of Red Phosphorus for Controlled Synthesis of Polyphosphides

Red Phosphorus: An Up-and-Coming Photocatalyst on the Horizon for Sustainable Energy Development and Environmental Remediation

Elemental Phosphorus and Electromagnetic Radiation

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