Thiophosphoryl Fluoride Research Articles

ChemInform Abstract: Reaction of Phosphorus Trifluoride and Thiophosphoryl Fluoride with Iodine Monochloride and Oxidation of Phosphorus Trifluoride with Nitryl Chloride, Iodic Acid, Periodic Acid, Sodium Nitrite, and Potassium Nitrite.

ChemInform Abstract: Reaction of Phosphorus Trifluoride and Thiophosphoryl Fluoride with Iodine Monochloride and Oxidation of Phosphorus Trifluoride with Nitryl Chloride, Iodic Acid, Periodic Acid, Sodium Nitrite, and Potassium Nitrite.

MNDO-PM3 study on gas-phase alkaline hydrolysis of phosphoryl and thiophosphoryl fluorides

The gas-phase alkaline hydrolysis of phosphoryl and thiophosphoryl fluorides was theoretically examined by using the semiempirical MNDO-PM3 molecular orbital method. The potential-surface analysis showed that the facial attack of the hydroxide ion from the backside toward one of the P–F bonds was thermodynamically favored. The three trigonal bipyramidal and one square pyramidal pentacoordinate species were specified as stable intermediates by a reaction coordinate method. The vibrational analysis of transition states demonstrated that these permutational isomers were interconverted by Berry's pseudorotation process. The larger activation enthalpy of permutation was required for most pentacoordinate species from thiophosphoryl fluoride through permutation than phosphoryl fluoride. The apical departure of the fluoride ion from the pentacoordinate species was enegetically most favorable.

Reaction of phosphorus trifluoride and thiophosphoryl fluoride with iodine monochloride and oxidation of phosphorus trifluoride with nitryl chloride, iodic acid, periodic acid, sodium nitrite and potassium nitrite

Phosphorus trifluoride and thiophosphoryl fluoride both react smoothly with iodine monochloride at room temperature to form dichlorotrifluorophosphorane. The oxidants, nitryl chloride, iodic acid and periodic acid undergo reduction to nitrosyl chloride and iodine respectively, oxidising the phosphorus trifluoride to phosphoryl fluoride. The nitrite salts of sodium and potassium also undergo reduction at elevated temperatures(200°C) with phosphorus trifluoride and then react further with the formed phosphoryl fluoride to yield the corresponding monofluorophosphates of sodium and potassium.

Reactions of phosphorus trifluoride and thiophosphoryl fluoride with strong oxidizing agents

Facile oxidations of phosphorus trifluoride occur yielding a pentavalent phosphorus compound upon reaction with iodine monochloride, nitryl chloride, iodic acid and periodic acid. Reactions with sodium and potassium nitrites yield phosphoryl fluoride as a primary reaction product which further reacts to form corresponding monofluorophosphates along with the metal fluoride. Reactions of thiophosphoryl fluoride with iodine monochloride resembles closely that of phosphorus trifluoride in the formation of dichlorotrifluorophosphorane with elemental sulphur formed in addition. No reaction is observed with nitryl chloride. Details of these reactions will be presented.

Reaction of thiophosphoryl fluoride with sulphur trioxide

Thiophosphoryl fluoride is observed to undergo a facile reaction with sulphur trioxide forming phosphoryl fluoride, sulphur dioxide and elemental sulphur in quantitative yields. In the presence of excess of sulphur trioxide, however, the elemental sulphur released combines with it to form sulphur sesquioxide which subsequently decomposes and gives off sulphur dioxide. Similar observations are made with oleum.

ChemInform Abstract: INFRARED BAND CONTOUR ANALYSIS AND MOLECULAR CONSTANTS OF THIOPHOSPHORYL FLUORIDE AND NITROGEN SULFIDE FLUORIDE (NSF3)

Chemischer InformationsdienstVolume 10, Issue 40 Physical Inorganic Chemistry ChemInform Abstract: INFRARED BAND CONTOUR ANALYSIS AND MOLECULAR CONSTANTS OF THIOPHOSPHORYL FLUORIDE AND NITROGEN SULFIDE FLUORIDE (NSF3) F. KOENIGER, F. KOENIGERSearch for more papers by this authorC. E. BLOM, C. E. BLOMSearch for more papers by this authorA. MUELLER, A. MUELLERSearch for more papers by this author F. KOENIGER, F. KOENIGERSearch for more papers by this authorC. E. BLOM, C. E. BLOMSearch for more papers by this authorA. MUELLER, A. MUELLERSearch for more papers by this author First published: October 2, 1979 https://doi.org/10.1002/chin.197940005AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume10, Issue40October 2, 1979 RelatedInformation

REACTION OF THIOPHOSPHORYL FLUORIDE AND THIOPHOSPHORYL CHLORIDE WITH DIMETHYL SULPHOXIDE

Abstract Solid complexes of thiophosphoryl fluoride and thiophosphoryl chloride with dimethyl sulphoxide (DMSO) have been prepared and characterized.

A New Method for the Preparation of Sulphuryl Chloro Fluoride

It has been observed that a suspension of sodium fluoride in boiling acetonitrile could be used for the preparation of fluorine compounds such as silicon tetrafluoride [1], thiophosphoryl fluoride [2], sulphur tetrafluoride [3,4], and fluorocyclophosphazenes [5]. This method, when adopted for the fluorination of sulphuryl chloride [6], it is observed that a mixture of sulphuryl fluoride and sulphuryl chloro fluoride is obtained. On the other hand, when lead fluoride is substituted for sodium fluoride, pure sulphuryl chloro fluoride is evolved. Based on this observation, a new method has been standardised for the preparation of a pure sample of sulphuryl chlorofluoride by fluorinating sulphuryl chloride by lead fluoride in acetonitrile medium.

Thiophosphoryl fluoride and phosphoryl fluoride as initiators for the polymerisation of tetrahydrofuran

Thiophosphoryl fluoride and phosphoryl fluoride have been found to initiate the polymerisation of tetrahydrofuran. The living polymer formed has a high molecular weight of the order of a million and the density is found to be between 0.98 - 1.02 g/cc. A cationic mechanism for the polymerisation has been proposed.

Reaction of thiophosphoryl fluoride with metals and metal oxides

Reaction of thiophosphoryl fluoride with metals and metal oxides

Hydrolysis of thiophosphoryl fluoride

The hydrolysis of thiophosphoryl fluoride has been studied both in acid and alkaline medium. The products are phosphate, fluoride and varying amounts of sulphide, sulphite, thiosulphate and elemental sulphur depending on experimental conditions. The probable mode of formation of the different sulphur species has been explained on the basis of sulphur in a higher oxidation state in the thiophosphoryl fluoride molecule.

Investigations on the preparation, oxidation and reduction reactions of thiophosphoryl fluoride

Pure thiophosphoryl fluoride has been prepared by the fluorination of thiophosphoryl chloride by sodium fluoride in acetonitrile medium. Oxidation of this phosphoryl fluoride by acidified chloramine-T ruptures the phosphorus-sulphur bond and oxidises the sulphur present to the hexavalent state. Anhydrous hydrogen iodide reduces the sulphur to hydrogen sulphide and phosphorus to the trivalent state.

19F and 31P magnetic shielding anisotropies and the F–P–F bond angle of PSF3 in a smectic liquid crystal solvent

The 19F and 31P magnetic shielding anisotropies of thiophosphoryl fluoride have been determined at a single temperature and in the smectic liquid crystal phase solely, using 4-n-octyloxybenzylidene-4′ amino acetophenone (OBAA) as an orienting solvent. Measurements of the F–P–F bond angle are also reported. The absolute sign of the indirect P–F spin–spin coupling constant is found to be negative, and the anisotropy in this quantity is assumed to be negligible. In addition, the 31P spectra of phosphorus trifluoride, dissolved in a smectic liquid crystal solvent, is also investigated in this study, and the value of Δσ obtained in the smectic phase for PF3 is found to be in disagreement with the previous value measured in the nematic liquid crystal phase.

Molecular structure of thiophosphoryl Fluoride as studied by gas electron diffraction

Abstract The molecular structure of SPF 3 has been determined by gas electron diffraction as follows: r g (PF) = 1.538 ± 0.003 A , r g (SP) = 1.866 ± 0. 005 A and α ) = 99.6 ± 0.3°. The uncertainties represent estimated limits of error. The observed bond lengths and angle for this molecule have been compared with those for related molecules, and empirical equations representing the phosphorus-halogen bond lengths and the valence angles of phosphorus and the other group Vb atoms are obtained.

On the vibrational assignment of thiophosphoryl fluoride

Normal coordinate calculations have been carried out for thiophosphoryl fluoride (SPF 3 ) using a simple valence force field and several modified valence force fields. These calculations have shown that the a 1 vibrations of SPF 3 cannot be assigned in a simple way to bending or stretching vibrations. The degenerate e vibrations on the other hand can be assigned to PF stretching FPF bending and SPF bending vibrations.

Vibrational Analysis of Thiophosphoryl Fluoride

Vibrational calculations have been made for thiophosphoryl fluoride, using a valence force field with nine parameters. The calculations support assignment of the 983-cm−1 band to the P–F3 symmetric stretch and assignment of the 698-cm−1 band to the P=S stretch.

Chemistry of phosphorus fluorides. Part III. The reaction of thiophosphoryl-fluoride with dimethylamine and some properties of the dimethylaminothio- phosphoryl fluorides

Dimethylamine reacts with thiophosphoryl fluoride with non-integral stoichiometry to yield the volatile compound dimethylaminothiophosphoryldifluoride and the solid products contained hexafluoro-phosphate and difluorodithiophosphate ions, and an unstable complex ion containing phosphorus and fluorine. The reaction of dimethylaminothiophosphoryldifluoride with dimethylamine to form bis-(dimethylamino)thiophosphorylfluoride has also been studied. The solid residues of this reaction contained hexafluorophosphate and difluorodithiophosphate ions and an unidentified phosphorus-fluoride salt. Dimethylaminothiophosphoryldifluoride did not complex with boron trifluoride but reacted with hydrogen halides to yield the halogenothiophosphoryldifluorides. Physical and spectroscopic data on the alkylaminothiophosphoryl fluorides are reported.

The infrared spectrum of thiophosphoryl fluoride

Investigation of the infrared spectrum of thiophosphoryl fluoride has indicated the following fundamental vibrations: 275, 404, 442, 698, 951 and 983 cm −1. The lowest three frequencies are assigned to deformation modes, the 698 cm −1 band is assigned to the symmetric PF stretch, the 951 cm −1 band to the antisymmetric PF stretch, and the 983 cm −1 band is assigned to the symmetric PS stretching vibration. New thermodynamic functions have been calculated.

Synthesis of Thiophosphoryl Difluoride Isothiocyanate and Thiophosphoryl Fluoride Diisothiocyanate

Synthesis of Thiophosphoryl Difluoride Isothiocyanate and Thiophosphoryl Fluoride Diisothiocyanate