Table of contents

The applications of the method of photoelectron spectroscopy in the study of the electronic and steric structures of organophosphorus compounds is examined. The spectra of two-, three-, and four-coordinated phosphorus are interpreted in terms of the approximation of Koopmans' theorem. Attention is concentrated on the elucidation of the composition of the upper occupied orbitals. The manifestations of the n–π and n–n interactions in the photo-electron spectra of these compounds are investigated. The bibliography includes 104 references.

The results of research on the steric and electronic structures of organophosphorus compounds with the aid of the Kerr effect and the combined employment of the Kerr effect and other physical methods (dipole moments, depolarisation of Rayleigh light scattering, spectroscopic methods) are surveyed. The additive refractions, polarities and polarisabilities of phosphorus bonds are analysed and data are presented on the conformational analysis of acyclic phosphorus-containing molecules and four-, five-, and six-membered phosphorus-containing heterocycles. The bibliography includes 130 references.

The available information about the kinetics of the hydrolysis of phosphate esters in neutral, alkaline, and acidic media is considered and the mechanisms of the hydrolysis of various reactive forms of mono-, di-, and tri-esters are discussed. A systematic account is given of the rate constants, taking into account the type of ester and its reactive form. The bibliography includes 106 references.

The literature data on the methods of preparation, structures, and properties of phosphorus nitrides PN, poly(phosphorus nitrides) (PN), (P₃N₅), etc., poly(phosphorus oxynitride) (NPO), and its thio-analogue (NPS) are surveyed and their practical applications, in particular as unique starting materials, formed as a result of the direct binding of molecular nitrogen, in the manufacture of phosphorus-nitrogen fertilisers are examined. The bibliography inciudes 169 references.

Work during recent years on the synthesis and investigation of 5,10-dihydrophenophosphazines is summarised. It is suggested that these compounds containing tervalent phosphorus may be of interest as pharmacological preparations. A complete list of 5,10-dihydrophenophosphazines synthesised by 1976 is given, together with 40 references.

The structure and the chemical behaviour of thio-esters of three-coordinated phosphorus R_nP(SR')_3–n (n = 0–2) are examined, and their reactions are discussed with electrophilic reagents differing both in the number and in the nature of the electrophilic centres. The peculiar character of such reactions is due primarily to the presence of two competing nucleophilic centres to the ambidenticity of the phosphorus(III)–sulphur(II) group, and to the high reactivity of two-coordinated sulphur (thionic and thiolic) in esters of three- and four-coordinated phosphorus. A list of 170 references is included.

Methods of preparation, problems of the establishment of structure and elementotropism, and chemical reactions are surveyed on the basis of 177 references.

The fundamental methods and applications of the chloromethylation of aromatic and hetero-aromatic compounds as well as ideas concerning the reaction mechanism are considered on the basis of data published mainly during the last ten–fifteen years. The bibliography includes 285 references.