Phosphorus organic derivatives

Phosphorus compounds exhibit an enormous variety of chemical and physical properties as a result of the wide range ia the oxidation states and coordination numbers for the phosphoms atom. The most commonly encountered phosphoms compounds are the oxide, haUde, sulfide, hydride, nitrogen, metal, and organic derivatives, all of which are of iadustrial importance. The hahde, hydride, and metal derivatives, and to a lesser extent the oxides and sulfides, are reactive iatermediates for forming phosphoms bonds with other elements. Phosphoms-containing compounds represented about 6—7% of the compound hstiugs ia Chemical Abstracts as of 1993 (1). 

Trifluoromethanesulfonic (triflic) anhydride is commercially available or can be prepared easily by the reaction of triflic acid with phosphorus pentoxide [66] This moderately hygroscopic colorless liquid is a useful reagent for the preparation of various organic derivatives of triflic acid A large variety of organic ionic triflates can be prepared from triflic anhydride A recent example is the preparation of unusual oxo-bridged dicatiomc salts of different types [SS, 89, 90, 91, 92, 93] (equations 38-44) Stabilized dication ether salts of the Huckel aromatic system and some other systems (equations 38 and 39) can be prepared in one step by the... 

Metallophosphazenes with Phosphorus-Metal Bonds. Until recently, the chemistry of cyclic and high polymeric phosphazenes was essentially the chemistry of their organic derivatives (Scheme 1). However, a discovery reported in 1979 (31) opened up a new field of metallophosphazene chemistry in which transition metals form the nucleus of the side group structure and are linked to the skeleton through phosphorus-metal bonds. These species are of theoretical and potentially practical importance, and I will summarize briefly some of the main features known at this time. 

The possibility of orbital reorganization in ion-radicals should be taken into account. Thus, organic derivatives of three-valence phosphorus exist in the sp hybrid state and an electron is removed from one of these orbitals. The cation-radical formed can retain the initial orbital configuration, but can also convert into the sp d hybrid state. In the latter case, one additional orbital of the phosphorus atom becomes accessible for the reactant attack. If Y—H bond in the reactant is weak, the reaction R3P+ -f YH proceeds with the participation of an sp frontal orbital according to the radical mechanism. Thiols are typical reactants with the weak Y—H bonds. If anions (A ) react with RjP, the vacant sp d orbital of the phosphorus appears to be a target. Scheme 3.14 illustrates the orbital pictures and the reaction directions. 

Organic derivatives of phosphorus excel by the strong tendency of trivalent phosphorus to combine with oxygen or sulfur to form phosphine oxides and phosphates or their sulfur analogs. 

Carbon is, of course, unique in the number of hydrides it forms, but the elements in the proximity of carbon in the Periodic Table have a similar, if more restricted, propensity to form hydrides. Silicon, germanium, boron and phosphorus are obvious examples. For hydrides of these elements, and especially for their organic derivatives, the methods of substitutive nomenclature can be applied to obtain suitable names. 

Organic derivatives of phosphorus trichloride—i.e., chlorophosphines of the types RPC12 or R2PC1—had never been fluorinated. We assumed the hitherto unknown fluorophosphines to be possibly interesting ligands in coordination chemistry. Such expectations were supported by earlier observations of Chatt (5, 6) and Wilkinson (32), who found that the parent compound phosphorus trifluoride as a ligand in certain coordination compounds with platinum or nickel behaved very much like carbon monoxide. 

The study of organophosphorus chemistry began more than 130 years ago. However, these substances found practical application only after World War II. At present the most widespread application for organophosphorus compounds is pest control in agriculture. Biological activity is characteristic of the following derivatives of phosphorus organic acids ... 

Another class of inclusion complexes containing phosphorus in the host structure are cyclophosphazenes. Sozzani and co-workers have reported 31P CP/MAS studies of two organic derivatives tris(o-phenylene-dioxy)cyclotriphosphazene (TPP) and tris(2,3-naphtalene-dioxy)cyclotri-phosphazene (TNP). In the cited works, SS NMR technique was employed to recognise guest-free TNP matrix and of ICs with guests, for example benzene, tetrahydrofuran and p-xylene. The 31P NMR spectra were particularly informative regarding the symmetry of the phos-phazene ring. 

Sulfide oxidation and sulfate reduction are reactions that are usually microbially mediated in Earth-surface environments. It is likely that this is also true of subglacial environments. If this is the case, there is a requirement for nutrients, such as nitrogen and phosphorus. Snow- and ice melt provide limited quantities of nitrogen, mainly as NOJ and NH4, and it is likely that phosphorus is derived from comminuted rock debris. However, there may well be a rock source of NH4 from mica and feldspar dissolution (Holloway et al., 1998), and some may also be obtained from the oxidation of organic matter. The concentration of NOJ in glacial runoff is usually <30 p,eq L, and often between 0 p,eq and 2 peq L. On occasion, NO concentrations are below the detection limit, which may be evidence for microbial uptake in subglacial environments. 

The organic derivatives of P, As, Sb and Bi have been the subject of a large number of mass spectrometric investigations. References for these works can be found in the periodical Mass Spectrometry. The mass spectral characteristics of these compounds, the most studied of which are the phosphorus derivatives, have also been reviewed . ... 

Further changes adsorption characteristics of high-silica zeolite of pentasil type and ultrastable form Y zeolite modified by boron and phosphorus, both from aqueous solutions of appropriate acids and by treating of organic derivative vapors were consideration. 

Modifying and stabilizing influence phosphonate in relation to polymeric materials is investigated to a lesser degree, than others organic derivative the four-co-ordinates phosphorus. 

The phosphoryl fluorides are a source of many inorganic and organic derivatives.16,17 The easy cleavage of a phosphorus-chlorine or phosphorus-bromine bond is responsible for the synthetic utility of the compounds. 

Although organic derivatives of the type [MR4]+X are well known for M = P, As and Sb (sec page 390), only phosphorus gives the hydrogen-containing prototype, PH4, and this does not form any very stable compounds. As noted in Section 13-4, the proton affinity of PH3 is substantially less than that of NH3. The PH4 ion is tetrahedral45 with P—H = 1.414 A as... 

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