Lidiya I. Kursheva

Conformations and coordination properties of trialkyltrithiophosphites in copper(I) complexes

A series of complexes (RS)3P·CuBr with Ra Et, Pr, Bu, i-Pr as well as the complex of (PrS)3P·CuSCN were studied by X-ray single-crystal diffraction. Coordination properties of thiophosphites were found to be essentially different from their oxygen and nitrogen analogues and depend on the nature of the metal center, substituents at sulfur atoms, the conditions of reactions and of the crystal growth. All trithiophosphites in the studied copper(I) complexes except the isopropyl derivative exhibit bidentate coordination with both phosphorus and sulfur participating in coordination bonds with copper. Trithiophosphites increase their conformational multiformity upon complexation regardless of the coordination mode, propyl and butyl derivatives being conformationally inhomogeneous in crystals. Unusual cis-conformations about the P‐S bond, which are not observed for “free” trialkyltrithiophosphites or their phosphoryl and thiophosphoryl analogues, are realized in the complexes. The complexation results in the significant high-frequency shift of the symmetric and asymmetric PS3 stretching vibrations in the Raman spectra of complexes regardless of the coordination mode and in minor changes of the C‐S stretching vibrations in comparison with the spectra of the “free” ligands. q 2000 Elsevier Science B.V. All rights reserved.

Triisopropyl phosphorotrithioite as a monodantate and a tridentate ligand in complexes with copper(I) halides

Triisopropyl phosphorotrithioite reacts with copper(I) halides to form complexes (i-PrS)3P·CuX (X = I, Br, Cl) of a cubic structure with monodentate coordination by the Cu···P bond. The complex [(i-PrS)3P·4CuCl]n is formed by disproportionation of diisopropyl phosphorochloridodithioite and has an unusual structure comprising a two-dimensional net of (CuCl)8 clusters bridged by triisopropyl phosphorotrithioite ligands; a tridentate coordination by one P(III) and two S(II) atoms was first observed in the complex.

New Method for the Synthesis of Ammonium Salts of O,O′-Dialkyldithiophosphoric Acids on the Basis of Elemental Phosphorus and Sulfur—A Method for the Preparation of Effective Inhibitors for Carbon Dioxide Corrosion of Mild Steel

Abstract New ammonium salts of O,O′-dialkyldithiophosphoric acids have been obtained based by the reaction of white phosphorus (P4)–alcohol–amine–elemental sulfur. The reaction is characterized by full conversion of white phosphorus and is not accompanied by the release of hydrogen sulfide. It has been established that all studied compounds are highly efficient inhibitors of CO2-mediated corrosion of mild steel active at concentrations of 0.25–5 mg·L−1.

New Method for the Preparation of Octathiotetraphosphetanes on the Basis of Elemental Phosphorus and Sulfur: Structure and Properties

Abstract New octathiotetraphosphetane ammonium salts are obtained based on the reaction of white phosphorus (Р4) and elemental sulfur with aliphatic mercaptans in the presence of amines (morpholine, methylmorpholine, pyrrolidine, and N,N-dimethylbenzylamine). The salts of octathiotetraphosphetane are characterized by IR/Raman spectroscopy. Several common IR and Raman bands can be used as structural markers for establishing the structures of [P4S8]4− anion in new compounds.

O,O-Dialkyldithiophosphoric Acids in the Reactions with Nonactivated α-Olefins

Abstract Reactions of O,O-dialkyl dithiophosphoric acids with hexadec-1-ene, octadec-1-ene, and also 2-methylpentadec-1-ene and 2-methylheptadec-1-ene as impurities in commercial samples of hexadec-1-ene and octadec-1-ene, and pure 2-methylpent-1-ene were studied in the presence of zinc chloride and ultrasound irradiation. GRAPHICAL ABSTRACT

Coordination Features of P,S-Ligands Based on the Phosphorus Derivatives with I and Viii Group Metals

Abstract Continuing the study of the coordination ability of P,S-ligands, we have investigated the behavior of some P(IV)-S-phosphorus derivatives, in particular, trialkyltetrathiophosphates (R = i-Pr, Bu) and piperidinium and triethylammonium salts of octathiotetraphosphetane in reaction with Cu(I), Ag(I), Co(II), and Fe(II) halides. The series of complexes were obtained and characterized by the X-ray single crystal diffraction and IR/Raman spectroscopy. GRAPHICAL ABSTRACT

Novel Effectively Carbonaceous and Sulfurated Hydrogen Corrosion Inhibitors on the Basis of Organosulfurphosphorus Compounds

Abstract Novel ammonium salts of O,O-dialkyl dithiophosphoric acids were obtained by one-pot synthesis from white phosphorus, elemental sulfur, industrial alcohols or phenols, and amines. Long-chain S-alkyl O,O-dialkyldithiophosphonates were prepared by the reaction of red phosphorus with elemental sulfur, alcohols, and the cheap industrial fractions of С16–С18 and С20–С26 of higher α-olefins in the presence of Lewis acid catalyst. The dithiophosphates obtained possess the high anticorrosion activities toward mild steel. GRAPHICAL ABSTRACT

Novel Approach to the Synthesis of Phosphorus Sulfur Organic Compounds and Their Metal Complexes

Abstract The reaction of elemental phosphorus (Pti 4) and sulfur with protonodonor reagents (alcohols, phenols, and thiols) has been studied in the presence of amines and complexes based on trialkyltrithiophosphites and transition metal halides. A novel approach to the synthesis of phosphorus sulfur organic compounds has been proposed on the basis of these reactions.

Synthesis of Organophosphorus Compounds in Terms of Elemental Phosphorus, Sulfur and their Derivatives

We have developed new facile methods for synthesizing various organophosphorus compouds on the basis of elemental phosphorus and sulfur, phosphorus sulfides and esters of thiophosphorous acids.

COMPETITIVE COORDINATION OF METALS BY PHOSPHORUS AND SULFUR IN COMPLEXES WITH POLYDENTATE LIGANDS CONTAINING P(III)-S BONDS

A series of complexes of thiophosphites with transition metals has been studied by X-ray single crystal diffraction: CuHalLP(SR)3, CuHalLP(SR)3LNCMe, CuBrLP(SEt)2NEt2, CuSCNLP(SR)3, CpMn(CO)2LP(SR)3, ArCr(CO)2LP(SR)3, with Hal = Cl, Br, I and R = Me, Et, Pr, i-Pr, Bu, Ph. Depending on the metal center, substituents R at sulfur, the conditions of reactions and crystal growth, different coordination modes have been observed: “classical” monodentate binding via phosphorus, unusual bidentate mode with participation of both P and S donor atoms of the ambident P – S system, as well as both monodentate and bidentate modes in one complex.