Tricoordinated Phosphorus Compounds Research Articles

Addition reactions of a phosphorus triamide to nitrosoarenes and acylpyridines

Tricoordinate phosphorus compounds react with a wide variety of double bonds through addition reactions. The dipolar and cyclic products formed are important intermediates in organophosphorus chemistry. We investigated the reactivity between phosphorus triamide 1 and nitrosoarenes and 2-acylpyridines. For sterically congested substrates, the formation of σ5,λ5-phosphorus products is observed. DFT calculations indicate this product is formed through a concerted [4 + 1] mechanism. For less sterically congested substrates, products are observed arising from cleavage of the N = O or C = O bond with formation of a terminal P = O bond and aryl nitrene or carbene migration into a P–N bond of the phosphorus triamide core. DFT calculations are consistent with an initial [2 + 1] addition to phosphorus followed by formal carbene/nitrene migration in these cases.

ChemInform Abstract: Applications of Tricoordinated Phosphorus Compounds in Organocatalysis

AbstractReview: 142 refs.

ChemInform Abstract: Applications of Tricoordinated Phosphorus Compounds in Homogeneous Catalysis

AbstractReview: 320 refs.

ChemInform Abstract: Tricoordinate Phosphorus Compounds as Catalysts for the Isomerization of (Z)- to (E)-Azobenzene.

ChemInform Abstract: Tricoordinate Phosphorus Compounds as Catalysts for the Isomerization of (Z)- to (E)-Azobenzene.

State of the Art: Chemical Synthesis of Biophosphates and Their Analogues via PIII Derivatives

AbstractFor Abstract see ChemInform Abstract in Full Text.

THE KINETICS AND MECHANISM OF THE REACTION OF TRICOORDINATE PHOSPHORUS COMPOUNDS WITH SULFENATE ESTERS

The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds, ArnP(OCH2CF3)3-n with arylsulfenate esters, ArSOCH2CF3, are reported. Product analysis, kinetic order, activation parameters, Hammett data and solvent effects are the criteria used to elucidate the two step mechanism involving arylthiophosphoranes as intermediates.

THE KINETICS AND MECHANISM OF THE REACTION OF TRICO-ORDINATE PHOSPHORUS COMPOUNDS WITH TETRACYANOQUINODIMETHANE AND TETRACYANOETHYLENE

Abstract Trico-ordinate phosphorus compounds, ArηP(OPri)3-η where n = 0–3, react with tetracyanoquino-dimethane (TCNQ) in acetonitrile in the presence of water to give the corresponding phosphoryl compounds, ArηP(O)(OPri)3-η and 1,4-bis-dicyanomethylbenzene (TCNQH2) in quantitative yield. The kinetics of these reactions are reported together with the Hammett ρ-parameters from variation of substituents in the aryl group for n = 1,2 and 3. On the basis of the available evidence, a mechanism is proposed involving one electron transfer from phosphorus (the donor) to TCNQ. A kinetic study of the reaction of triarylphosphines with TCNE in aqueous acetonitrile, however, suggests rate-limiting nucleophilic attack on nitrogen rather than the radical cation mechanism.

Organophosphorus Transition Metal Chemistry: Palladium Catalyzed Arylation of Tetra- and Tricoordinated Phosphorus Compounds

Abstract A large variety of usefully functionalized α,β-unsaturated phosphine oxides (including bifunctional and homochiral ones), functionalized tetraaryl phosphonium salts and the C-P heterocyclic systems can be obtained directly by means of the Pd - catalyzed arylation of vinyl phosphine oxides, arylation of tertiary phosphines and aryl exchange processes in quaternary phosphonium salts.

ChemInform Abstract: Reaction of Tricoordinate Phosphorus Compounds with Organophosphorus Pseudohalogens. Part 1. Desulfurization and Deoxygenation of Oxophosphoranesulfenyl Chlorides. Scope and Mechanism.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reactions of trico-ordinate phosphorus compounds with phosphorus pseudohalogens. Part 2. Pentaco-ordinate intermediates in the reaction of o-phenylene neopentyl phosphite with diethoxyoxophosphoranesulfenyl chloride

Reaction between oxophosphoranesulfenyl chloride 1(R = R′= EtO) and o-phenylene neopentyl phosphite 4 takes predominantly the deoxygenation course, yielding the phosphorochloridothioate 7 and the phosphate 8. Formation of minor products 5 and 6 corresponding to the desulfurization pathway, and low-temperature 31P NMR observations, are rationalized by proposing phosphoranephosphonium equilibria which are shifted towards phosphorane structures 9, 13, 11. These results supplement our earlier studies on desulfurization and deoxygenation of compound 1 with tricoordinate phosphorus compounds and add new evidence for phosphonium–phosphorane equilibria.

Réactions De P‐Phényl C‐Amino Alkylidenephosphines Avec Les Diazocomposes

AbstractP‐Phenyl C‐aminophosphaalkenes 1 react with some disubstituted diazocompounds at −20°C leading to tricoordinated phosphorus compounds 2, 9, 11 and 12 via a Staudinger type reaction. These compounds decompose already at room temperature and quickly by heating. Azines are isolated after extrusion of phenyl phosphinidene.

ChemInform Abstract: The Kinetics and Mechanism of the Reaction of Tricoordinate Phosphorus Compounds with Diaryl Trisulfides

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reaction of tricoordinate phosphorus compounds with organophosphorus pseudohalogens. 1. Desulfurization and deoxygenation of oxophosphoranesulfenyl chlorides. Scope and mechanism

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReaction of tricoordinate phosphorus compounds with organophosphorus pseudohalogens. 1. Desulfurization and deoxygenation of oxophosphoranesulfenyl chlorides. Scope and mechanismE. Krawczyk, J. Mikolajczak, A. Skowronska, and J. MichalskiCite this: J. Org. Chem. 1992, 57, 18, 4963–4970Publication Date (Print):August 1, 1992Publication History Published online1 May 2002Published inissue 1 August 1992https://doi.org/10.1021/jo00044a035RIGHTS & PERMISSIONSArticle Views454Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (899 KB) Get e-Alerts Get e-Alerts

The kinetics and mechanism of the reaction of tricoordinate phosphorus compounds with diaryl trisulfides

Kinetic data and activation parameters are reported for the reaction of a series of tricoordinate phosphorus compounds, [ArnP(OR)3–n], with diaryl trisulfides. The second-order rate coefficients for series of arylphosphines, phosphinites and phosphonites, correlate with the Hammett σ constants of the aryl substituents with ρ values of –1.1, –1.1 and –1.1 respectively and these results are discussed in terms of a biphilic mechanism analogous to that proposed for the reaction of tricoordinate phosphorus with S8.

THE REACTIONS OF 1,2,3-DIAZAPHOSPHOLE DERIVATIVES WITH CATECHOL

Abstract Both two-coordinated phosphorus compounds and tri-coordinated phosphorus compounds reacted with catechol in the presence of triethylamine to yield hexa-coordinated phosphorus compound 3 were confirmed by elemental analysis, IR, 31P NMR and MS. The mechanism of these reactions was suggested.

Trico-ordinate phosphorus compounds as catalysts for the isomerization of (Z)-to (E)-azobenzene

The isomerization of (Z)-azobenzene to (E)-azobenzene is catalysed by trico-ordinate phosphorus compounds, ArnP(OR)3 –n where n= 0–2. The reaction is overall second order and for n= 1 and 2, the ρ values of –0.55 and –0.45, respectively, indicate a low degree of charge separation in the transition state. Solvent effects confirm this conclusion and relative rates for n= 0–3 suggest that the transition state is a hybrid of biphilic and polar components.

ChemInform Abstract: Monocyclic Phosphoranes with PH Bonds in the Ligand Redistribution Reaction of Tricoordinated Phosphorus Compounds.

AbstractThe reaction of phospholanes such as (I) with nucleophiles such as (II) is studied.

ChemInform Abstract: Phosphoranes Formed from the Condensaton of Tricoordinate Phosphorus Compounds with Phenanthraquinone.

AbstractPhenanthrenequinone (I) and the phosphorus compounds (II) are combined to form the adducts (III) which are directly characterized by NMR spectroscopic methods.

PHOSPHORANES FORMED FROM THE CONDENSATION OF TRICO-ORDINATE PHOSPHORUS COMPOUNDS WITH PHENANATHRAQUINONE

Abstract The synthesis of a range of monocyclic and bicyclic phosphoranes from the condensation of trico-ordinate phosphorus compounds with phenanthraquinone is reported together with their 31P, 1H and 13C nmr data. The phosphorus chemical shifts of these compounds range from +34 to -35 ppm but solvent effects on [sgrave]P and the retention of P–C coupling throughout the range indicate that all of these compounds are true phosphoranes.

NEW TRI-COORDINATED AND PENTACOORDINATED PHOSPHORUS COMPOUNDS AND A BORON SPIRANE INVOLVING AN ENOLPYRUVATE MOIETY. SYNTHESIS OF A HYDROXYPHOSPHORANE MODEL OF INTERMEDIATE PHOSPHORANES IN NUCLEOPHILIC SUBSTITUTION REACTIONS ON PHOSPHORIC ESTERS OF ENOLPYRUVIC ACID

Abstract Hydrido and hydroxyspirophosphoranes, cyclic tri-coordinated phosphorus compounds and a boron spirane involving a phenylenolpyruvate moiety were prepared from reactions between phenylpyruvic acid and phosphorus trichloride, or (and) chloro-2-dioxaphospholane 1,3,2, or (and) chloro-2-oxo-2-phenyl-4,5-dioxaphospholane 1,3,2, or (and) boric acid. The hydroxyphosphorane is a good model of the intermediate postulated in the hydrolysis of enolpyruvate phosphoric esters.