Tricoordinated Phosphorus Compounds Research Articles

Kinetics and mechanism of the reaction of trico-ordinate phosphorus compounds with octasulphur

Kinetic data and activation Parameters are reported for the reactions of a series of phosphites, arylphosphonites, diarylphosphinites, and triarylphosphines with octasulphur (S8) in toluene as solvent. For the Phosphites the data are explained in terms of changes in p-character of the lone-pair orbital on Phosphorus and inductive electron donation by the alkyl groups. The rates of reaction of series of arylphosphonites, diarylphosphinites, and triarylphosphines correlate with the Hammett σ constants to give ρ values of –3.0, –3.0, and –2.5, respectively, and the results are discussed in terms of the Reactivity–Selectivity Principle and the biphilic mechanism for insertion of trico-ordinate phosphorus Into σ-bonds.

Reaction of Tricoordinate Phosphorus Compounds with Pseudohalogens. Scope and Mechanism

Abstract The selectivity of sulphur, selenium and oxygen removal from pseudohalogens: phosphorus disulphides 1 and 2, diselenides 3 and oxophosphoranesulphenyl chlorides 4 has been investigated. A mechanistic rationalization is proposed to account for sulphur (selenium)/oxygen extrusion variation as a function of substrates structure and reaction conditions.

PENTACO-ORDINATE PHOSPHORUS COMPOUNDS BY NUCLEOPHILIC ADDITION TO ACTIVATED ALKENES AND ALKYNES IN THE PRESENCE OF ALCOHOLS AND PHENOLS

Abstract The reactions of a variety of trico-ordinate phosphorus compounds, Ar n P(OR)3-n (n = 1 or 2), and cyclic analogues, with acrylonitrile, ethyl acrylate or ethyl phenylpropiolate and alcohols or phenols in low polarity media gives rise to a wide range of pentaco-ordinate phosphorus compounds. Attempts to extend this synthetic route to phosphoranes containing P[sbnd]N or P[sbnd]S bonds met with no success.

The reaction of 1-substituted 3,4-dimethyl-Δ3-phospholens with diethyl peroxide: a correlation between rate and31P nuclear magnetic resonance shift

The reactions of a variety of 1-X-3,4-dimethyl-Δ3-phospholens (where X = Br, Me, Ph, NMe2, SEt, H, and OR) with diethyl peroxide are described. The rates of reaction show a broad correlation with the 31P n.m.r. chemical shifts of the starting phospholens, with low field shifts corresponding to the highest reactivity. The results are discussed in terms of the biphilic mechanism for the reaction of trico-ordinate phosphorus compounds with weak σ-bonds.

Arylation catalytique d'organophosphorés. Produits de l'arylation, catalysée par les sels de nickel (II), de composés du phosphore tricoordiné.

Analysis of the products from the nickel (II) bromide catalysed arylation of tricoordinated phosphorus compounds R 2P-Z (Z  H, Cl, SR, NR 2 pointed out that this arylation always takes place on phosphorus resulting at first in formation of pseudophosphonium salts. Only the aminophosphonium salts are stable under reaction conditions; the other salts undergo several transformations which can be brought together in a general reactivity scheme to account for all the side products. On regard to other heteroatoms these results point out a particular ability of phosphorus to be arylated under nickel (II) catalysis. The reaction with secondary phosphines can be applied to synthetise diarylphosphonium salts.

Pentaco-ordinate phosphorus compounds by nucleophilic addition to activated alkenes

The reactions between a variety of trico-ordinate phosphorus compounds and acrylonitrile or ethyl acrylate provide a novel route to pentaco-ordinate phosphorus compounds.

Formation of stable cyclic dicoordinated phosphorus compounds by reaction of cyclophosphazanes with lewis acids

Thermal equilibrium between dicoordinated and tricoordinated phosphorus compounds (i.e. benzodiazaphosphole ⇄cyclotetraphosphazane) has been observed. The dicoordinated compounds have been stabilized by complexing with Lewis acid and isolated.

ChemInform Abstract: 2,5‐DIHYDRO‐1,3,2‐OXAZAPHOSPH(V)OLES. PREPARATION AND PROPERTIES

AbstractDie Azidooxirane (I) liefern mit den Phosphinen (II) in Pentan oder Ether bei 0 bis 25°C die Oxazaphosphole (III).

2,5-Dihydro-1,3,2-oxazaphosph(V)oles. Preparation and properties

2,5-Dihydro-1,3,2-oxazaphosph(V)oles, prepared by reaction of 2-azido-oxirans with trico-ordinated phosphorus compounds, exhibit a trigonal bipyramidal structure with the sp2 nitrogen atom apical and the oxygen atom equatorial.

Mecanisme de formation et de transformation des spirophosphoranes—VI : Nouveaux spirophosphoranes obtenus par addition 1,4 de derives cycliques du phosphore trivalent sur des systemes α-di-insatures

Spirophosphoranes obtained by addition of tricoordinated phosphorus compounds on α diketones and α ethylenic ketones are discussed. Steric and electronegativity factors which determine the number of stable isomers are considered, but no interconversion mechanism is postulated. Phosphorus epimerization has been studied with compounds containing two centres of asymmetry.