Phosphorus, atomic structure

Phosphorus Compounds. Acyclic phosphorus compounds containing only one phosphorus atom, as well as compounds in which only a single phosphorus atom is in each of several functional groups, are named as derivatives of the parent structures listed in Table 1.12. Often these... 

The EPR spectra of the related 1,2,4,6,3,5-thiatriazadiphosphinyl radicals (3.20) reveal a distinctly different electronic structure.The observed spectrum consists of a quintet of triplets consistent with coupling of the unpaired electron with two equivalent nitrogen atoms and two equivalent phosphorus atoms [Fig. 3.4(a)]. This interpretation was confirmed by the observation that the quintet collapses to a 1 2 1 triplet when the nitrogen atoms in the ring are 99% N-enriched [Fig 3.4(b)]. Thus the spin delocalization does not extend to the unique nitrogen atom in the phosphorus-containing system 3.20. 

The heterocycles 13.1 are isolated as purple crystals (R = Mc3SiNH, Ph) or as a thermally unstable, purple oil (R = Me), which decomposes at room temperature to give 13.3 (R = Me, Ph). The structure of 13.1 (R = Ph) consists of a six-membered ring in which the phosphorus atom lies 0.26 A out of the S2N3 plane. The S-N bond lengths fall within a narrow... 

The diphosphadithiatetrazocines 13.2 (E = S) and 13.3 (E = S) contain one more R2PN unit in the ring than 13.1. The structure of the orange-red 1,3-isomer (13.2, E = S, R = Ph) consists of an essentially planar N3S2 unit with the two phosphorus atoms located on opposite sides of the plane." Like 13.1 this isomer forms a 1 1 adduct with norbornadiene via 1,3-addition across the sulfur atoms. 

Fe—Fe bond can be assigned structures 201 or 202 based on spectral data. The other product of this reaction is 193 (R = r-Bu), however, it is produced in minor amounts. Complexes 199 (R = R = r-Bu, R = Ph, R = r-Bu) were obtained. Reaction of 146 (M = Mo, R = Ph, R = R = Ft, R = r" = Me) with (benzyli-deneacetone)iron carbonyl gives rise to the bimetallic complex 200 (M = Mo), which reacts further with the free phosphole to form the bimetallic heteronuclear sandwich 203. The preferable coordination of the molybdenum atom to the dienic system of the second phosphole nucleus is rather unusual. The molybdenum atom is believed to have a greater tendency to coordinate via the trivalent phosphorus atom than via the dienic system. 

Bis(3,5-dimethylpyrazol-l-yl)cyclotriphosphazene containing phenyl substituents at the phosphorus atoms (R) reacts with molybdenum and tungsten hexacar-bonylstogive34(R = Ph M = Mo, W) [94JCS(D)63]. IfRj = N(Me)(CH2)20, compounds 34 (R2 = N(Me)(CH2)20 M = Mo, W) having better solubility in organic solvents are produced. Their structures show the novel tridentate NNN feature of the ligands. 

A transition structure model was proposed which accounts for the high selectiv-ities obtained for some of the substrates [80]. In the structure shown in Scheme 6.37 the two phosphorus atoms of the Tol-BINAP ligand and the two car-... 

Taking into account the high structural similarity of dppf and cdpp, their different influence on the reaction s selectivity has to be attributable to electronic effects. The electron density at the phosphorus atoms is significantly lower in the case of cdpp, due to the electron-withdrawing effect of the formal cobalt(III) central atom... 

PdP2, however, contains continuous chains of phosphorus atoms (with, as expected, planar 4-coordinate Pd) while PdP3 has the CoAs3 structure (P4 rings). 

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. 

Here the phosphorus atom has four shared electron pairs and one unshared pair, using five orbitals. (In PC15, eg, the transargononic phosphorus atom has five shared pairs in its outer shell.) However, because of the electroneutrality principle such a structure is allowed only for structure 1. Transargononic structures do not occur for first-row atoms, so this phenomenon is not found in NF3. These ideas concerning the bonding in NF3 and PF3 are implicit in the discussion by Marynick, Rosen and Liebman61 of the inversion barriers of these molecules. 

The phosphinimide phosphanes 42 [75b], which are similar to the acyclic diphosphazanes comprising of one nitrogen and phosphorus atom, when treated with AlMea, (Scheme 19), were found to coordinate to the P(III) center to yield the alane adducts 43 which were characterized by the P-NMR spectroscopy and structure elucidation of 43a. 

On the other hand the alkyl- or amino-substituted congeners should adopt a more classical structure, in which the twofold coordinated phosphorus atom is bent, 8b. A first hint of the cation was reported by mass-spectroscopic investigations [67]. The synthetic verification of this prediction starts from amino-substituted diphosphene 22 via protonation with CF3SO3H [68] (Scheme 15). 

Zwitterionic heterocyclic compounds with two phosphorus atoms of opposite charge and different coordination were a rarity 10 years ago. This field has emerged recently with the reports of a variety of new structures as shown in Schemes 12,13,and 14. Schevchenko and Schmutzler described a compound of... 

Studying the reactivity of lo, 2a -diphosphete 56 with o-chloranil, Bertrand and coworkers reported the synthesis of zwitterionic 57 in which the two phosphorus atoms are directly linked by a a bond (Scheme 13). Structural details of 57 were further obtained through a X-ray crystallographic analysis [70]. 

Many types of phosphorus-phosphorus bonds are known, but it is rare to find such bonds in hexacoordinated phosphorus compounds (with the exception of 57). Cavell reported in 1998 the reaction of PCI5 with phenylbis(o-(trimethyl-siloxy)phenyl)phosphane, yielding the corresponding bischelate 61 in decent yield (52%) [99]. The octahedral nature of the central phosphorus atom was unambiguously determined by X-ray structural analysis. Two short axial bonds (2.202 A) lie perpendicular to the pseudo-octahedral equatorial plane. 

The displacement of a ligand L from the phosphorus atom of a phosphoranyl radical can easily occur via a-scission of the L-P bond (Scheme 23). The fragmentation is a regiospecific process, i.e., the leaving group must be apical (Scheme 23) and it occurs via an intermediate o" structure (Fig. 5). 

During the last two decades, Bentrude et al. [70] has shown that phosphoranyl radicals exhibiting very slow a- and P-fragmentations react with alkyl disulfides via Sh2 homolytic substitution (Scheme 35) [70b]. The reactivity of phosphoranyl radicals in these Sh2 reactions depends strongly on the substituents attached to the phosphorus atom and on the structure of the disulfides [70c]. 

A major feature of the polyphosphazene skeleton is its ability to resist fire and combustion due to the inorganic elements constitutive of its structure [44,387, 388,459,460]. Moreover, the action of skeletal nitrogen and phosphorus atoms can be enhanced by inserting additional inorganic elements (F, Cl, Br, J, B, metals, etc.) in the substituent groups [459,460]. 

Although the inner phosphorus atom has its octet of electrons, a formal charge calculation indicates that we can shift electrons to optimize the provisional structure ... 

The Lewis structure of phosphine shows three P—H bonds and one lone pair on the phosphorus atom. 

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