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Journal ArticleDOI

Catalytic Synthesis of Triaryl Phosphates from White Phosphorus

Kenneth Mark Armstrong, +1 more
- 01 May 2011 - 
- Vol. 2011, Iss: 13, pp 2138-2147
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TLDR
In this article, triaryl phosphates were synthesized from white phosphorus and phenols under aerobic conditions and in the presence of iron catalysts and iodine, and the reaction proceeds by formation of PI3, then O=PI(OPh)2 before the final formation of the phosphate.
Abstract
Triaryl phosphates were synthesized from white phosphorus and phenols under aerobic conditions and in the presence of iron catalysts and iodine Full conversion to phosphates was achieved without the use of chlorine, and the reactions do not produce acid waste Triphenyl phosphate, tritolyl phosphate and tris(2,4-di-tert-butyl)phenyl phosphate were synthesized by this method with high selectivities Various iron(III) diketonates were used to catalyze the conversion Mechanistic studies showed that the reaction proceeds by formation of PI3, then O=PI(OPh)2 before the final formation of the phosphate The nucleophilic substitution of O=PI(OPh)2 with phenol to form O=P(OPh)3 was found to be the rate-limiting step

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Journal ArticleDOI

Coordination chemistry of elemental phosphorus

TL;DR: In this article, a review comprehensively covers the coordination chemistry of elemental phosphorus during the years 2011-2020. The main part is dedicated to the activation of white phosphorus mediated by early and late transition metals and its subsequent reactivity once in the coordination sphere of a metal.
Journal ArticleDOI

Iodine Activation of Coordinated White Phosphorus: Formation and Transformation of 1,3‐Dihydride‐2‐iodidecyclotetraphosphane

TL;DR: Double stabilization: Previously unknown polyphosphorus compounds are obtained by activation of white phosphorus coordinated between two CpRu(PPh(3))(2) moieties with iodine, and subsequent hydrolysis.
Journal ArticleDOI

P4 functionalization by hydrides: direct synthesis of P-H bonds.

TL;DR: A direct method for white phosphorus functionalization by hydride sources is presented, which results in the formation of borane-stabilized phosphanide Li(PH2)(BEt3)2, which may be used to synthesize various phosphines.
Book ChapterDOI

Benign Chlorine-Free Approaches to Organophosphorus Compounds

TL;DR: In the quest for alternative environmentally benign technology, several routes have been envisaged starting either from elemental phosphorus or from one of its direct low-valent derivative as hypophosphite as discussed by the authors.
Journal ArticleDOI

Diphenyl Diselenide-Catalyzed Synthesis of Triaryl Phosphites and Triaryl Phosphates from White Phosphorus.

TL;DR: In this paper, a diphenyl diselenide-catalyzed one-step procedure involving white phosphorus and phenols, which provides a halogen- and transition metal-free way to these compounds, is described.
References
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Journal ArticleDOI

P4 Activation by Late-Transition Metal Complexes†‡

TL;DR: The coordination chemistry of white phosphorus is nowadays a mature discipline, which during the last four decades has reached a deep understanding of the mechanisms governing the metal-mediated activation of this unique and highly reactive molecule.
Journal ArticleDOI

Carbene-stabilized diphosphorus.

TL;DR: The potassium graphite reduction of L:PCl3 leads to the formation of carbene-stabilized diphosphorus molecules, L: P-P:L, 1 and 2 (L: = :C{N(2,4,6-Me3C6H2)CH}2), respectively, which were delineated by DFT computations.
Journal ArticleDOI

Soluble Allotropes of Main-Group Elements

TL;DR: Small clusters of main-group elements can be stabilized in the highly active zero oxidation state and used for reactions in solution.
Journal ArticleDOI

P4 Activation with [{Cp‘‘‘(OC)2Fe}2] (Cp‘‘‘ = C5H2But3-1,2,4): Exclusive Formation of the Exo/ Exo-Butterfly Complex [{Cp‘‘‘(OC)2Fe}2(μ-η1:η1-P4)]

TL;DR: The butterfly complex of white phosphorus, P4, in toluene gives the butterfly complex [{Cp‘‘(OC)2Fe}2(μ-η1:η 1-P4)] as mentioned in this paper.
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