Phosphorus molecular structure

Phosphorus-containing anionics are special surfactants with special properties. The variety of possible molecular structures makes possible a variety of properties and effects as well. 

Phosphorus-containing surfactants are amphiphilic molecules, exhibiting the same surface-active properties as other surfactants. That means that they reduce the surface tension of water and aqueous solutions, are adsorbed at interfaces, form foam, and are able to build micelles in the bulk phase. On account of the many possibilities for alteration of molecular structure, the surface-active properties of phosphorus-containing surfactants cover a wide field of effects. Of main interest are those properties which can only be realized with difficulty or in some cases not at all by other surfactants. Often even quantitative differences are highly useful. 

Immiscible solvents like water and oil can be transformed by addition of solubilizers to single-phase solutions. Amphiphilic substances are known as effective solubilizers. Solubilization depends on the HLB of the components that ought to form a single phase and on the kind of solubilizer used. Phosphorus-containing surfactants with their variety of possible molecular structures are solubilizers that can be tailored to the task demanded. 

The analysis of phosphates and phosphonates is a considerably complex task due to the great variety of possible molecular structures. Phosphorus-containing anionics are nearly always available as mixtures dependent on the kind of synthesis carried out. For analytical separation the total amount of phosphorus in the molecule has to be ascertained. Thus, the organic and inorganic phosphorus is transformed to orthophosphoric acid by oxidation. The fusion of the substance is performed by the addition of 2 ml of concentrated sulfuric acid to — 100 mg of the substance. The black residue is then oxidized by a mixture of nitric acid and perchloric acid. The resulting orthophosphate can be determined at 8000 K by atom emission spectroscopy. The thermally excited phosphorus atoms emit a characteristic line at a wavelength of 178.23 nm. The extensity of the radiation is used for quantitative determination of the phosphorus content. 

Although non-exhaustive, this review shows that a large variety of new difunc-tionalized mixed phosphorus and sulfur molecular structures have been described during the last ten years. It also demonstrates that such compounds are powerful synthetic tools or building blocks and, in some cases, molecules (or precursors of more complex molecules) with potential biological activities. 

Reduction of 1-benzyl-3,4-dibromophospholan oxide (125) with tri-chlorosilane, followed by debromination, gave 1-benzylphosphole. Determination of the molecular structure by X-ray analysis showed slight puckering of the ring with retention of pyramidal configuration at phosphorus. ... 

Trzcinskabancroft, B., Knachel, H., Dudis, D., Delord, T.J. and Marler, D.O. (1985) Experimental And Theoretical-Studies Of Dinudear Gold(I) And Gold(II) Phosphorus Ylide Complexes - Oxidative Addition, Halide Exchange, And Structural-Properties Including The Crystal And Molecular-Structures Of [Au (CH2)2PPh2]2 And [Au(CH2)2PPh2]2(CH3) Bri. Journal of the American Chemical Society, 107(24), 6908-6915. 

The molecular structures of germaphosphenes (entries 10 and 11, Table I) show much the same characteristics as germanimines.19,20 They are planar about the germanium atom and the Ge=P double bond is about 8% shorter than its single-bond analog. The angle at phosphorus is smaller... 

The type of interaction and its chemical influence are determined by phosphorus and boron coordination, by the type of the fragment separating them, and by molecular structure. Thus, it is reasonable to classify P,B-containing heterocycles according to the type of fragment separating phosphorus and boron. 

The axial orbitals used by phosphorus in this molecule can be considered as dp in character (see Chapter 4), which means they have no s character, whereas the orbitals in equatorial positions are sp2 hybrids. As expected, the fluorine atoms are found in axial positions and the molecule is nonpolar. This illustration shows the value of dipole moments in predicting the details of molecular structure. Table 6.1 shows dipole moments for a large number of inorganic molecules. 

Elder, R.C., Florian, L.R., Kennedy, E.R., and Macomber, R.S., Phosphorus containing products from the reaction of propargyl alcohols with phosphorus trihalides. II. The crystal and molecular structure of 2-hydroxy-3,5-di-ferf-butyl-l,2-oxaphosphol-3-ene 2-oxide, /. Org. Chem., 38, 4177, 1973. 

X-Ray.—The crystal and molecular structure of tri-o-tolylphosphine, its oxide, sulphide, and selenide (125) have been compared. The mean P—C bond lengths appear to be determined by the n-electron density along the P—C bond and intramolecular steric interactions, d-Orbital participation was considered to be of little importance.152 X-Ray diffraction established the structure of diphosphinofumarate (126)153 and showed that the phospholanium iodide (127) has an envelope ring with the methyl group at the point of the flap.154 The bicyclic phosphonium bromide (128) has a distorted half-chair phosphorus-containing ring, one of the P—C bonds in the... 

Electron.—The determination of the molecular structure of phosphorus heterocycles by electron diffraction has been reviewed.176 The structures of trimethylphosphine oxide, and the corresponding sulphide in the gaseous phase, have been compared. The rotational freedom of the methyl group appears to be greater for the sulphide, which also has the longer P—C bonds, i.e. 181.8 pm for (144 Ch = S)and 180.9 pm for (144 Ch = O).177 The trifluoromethylphosphoranes (145) and (146) adopt the... 

Low valent transition metal centers coordinate preferentially to the phosphorus atom of azaphos-pholes, P-Coordinated complexes of 2,5-dimethyl-1,2,3-diazaphosphole with Cr(CO)5 (molecular structure in Table 2), W(CO)5, Fe(CO)4, MnC5H4Me(CO)2 yoJOM(i85)53>, and Pt(PPh3)3 <83JOM(256)375>, of 2,5-dimethyl-4-(dimethylthiophosphoryl)- <80CB2278> and 1,5-dimethyl-1,2,3-... 

The molecular structure of sila-heterocycles is reviewed <98MI649>. The Raman and infrared spectra of 1-chloro-l-methylsilabutane have been studied in detail <99MI399>. The first allenic coompoimds with both silicon and phosphorus doubly bonded (ArP C Si(Ph)Tip, Tip = 2,4,6-triisopropylphenyl) have been prepared and dimerised to give 38 and 39 in the ratio of 3 2 <99MI774>. 

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