An SCF study of P4O6 and P4O10

The electronic structures of the oxides P₄O₆ and P₄O₁₀ are calculated by the self-consistent molecular orbital method including all valence electrons and the 3d orbitals on phosphorus. It is found that the former molecule appears to be virtually non-polar whilst in the latter, the P-O (terminal) bonds are highly polar. The bond order matrix shows that the internal P-P bonding in the P₄ unit is not marked.     

ChemInform Abstract: Study of the P4O7, P4O6S,and P4O6Se Vibrational Spectra.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Discrete copper(I) clusters with Cu6P6Se6 and Cu6P4Se6 cores

The reactions of chalcogenophosphinites with copper(I) metal salts are shown to yield highly stable, multi-metallic copper-chalcogen based clusters with novel topologies.     

Study of the Geometrical Structure and the Vibrational Spectra of P4O8, P4O6S2, and P4O6Se2

In the present work the bonding situation within the P₄O₆X₂ (X = O, S and Se) series is analysed by means of the geometrical structures and the IR spectra of those molecules. The experimental data are obtained from pure P₄O₈ and P₄O₆Se₂ crystals which could be synthesized for the first time. The theoretical geometrical structures were obtained by employing the Hartree-Fock method in combination with a basis set of double ζ quality plus polarization functions. Theoretical vibrational spectra calculated with the same method were refined by using the Scaled Quantum Mechanical method proposed by Pulay. Our study shows that the doubly substituted compounds behave very similar to the monosubstituted molecules, e. g. shifts of the vibrational frequencies result mainly from the differences in the bond strengths of the P = X units and the different masses of the substituents, while the bonding situation within the P₄O₆ frame remains nearly unchanged within this series.     

ChemInform Abstract: Vibrational Analysis of P4O6 and P4O10.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Verbesserte Darstellung,Kristallzüchtung und Strukturanalyse von P4O6S2 und P4O6S3

Improved Syntheses, Crystal Growth, and Crystal Structure Determination of P₄O₆S₂ and P₄O₆S₃ Syntheses and single crystal growths of the title compounds are described. Both compounds crystallize in the space group P2₁/c (P₄O₆S₂: a = 11.293(4); b = 6.457(3); c = 11.588(4) Å; β = 90.29(2)°, 2 450 diffractometer data, R_w = 0.035/P₄O₆S₃: a = 15.611(5); b = 8,303(3); c = 9.697(4) Å; β = 127.12(2)°, 2 481 diffractometer data, R_w = 0.034). The structural data for the series P₄O₆S_n (n = 1 – 4) thus completed are compared to their oxide analogues P₄O₆O_n (n = 1 – 4). The changes in the geometry of the P₄O₆-cage in course of its successive oxidation are discussed.     

The Ring Acid,H6P6O12 and Ring Acid,H4P4O10 and Their Salts

Abstract

The hydrated salts of the acid H₆P₆O₁₂, Rb₆P₆O·aq and M₃P₆O₁₂·aq (M = Ca, Sr, Ba), that have so far been unknown, have been prepared and studied by X-ray methods, thermal analysis and molecular spectroscopy. It has been found that the anion structure exhibits a chair form with the D_3d symmetry. All the salts are stable at laboratory temperature and are completely decomposed on prolonged heating to 80°C prior to complete dehydration. The newly prepared salts of the acid H₄P₄O₁₀ involve Cs₄P₄0₁₀·1.5 H₂O, Tl₄P₄O₁₀, M₂P₄O₁₀·x H₂O (M = Cu, Ni, Co; x = 10, 2, 6, respectively), Na₂MP₄O₁₀·x H₂O (M = Cu, Ni, Co; x = 8, 8, 4, respectively). They have been studied using X-ray methods, thermal analysis, molecular and reflectance spectra and the magnetic susceptibility. The dehydration of the salts starts at 30 to 40°C and ends by complete decomposition before the completion of dehydration at 150°C. The anion structure for the salt CS₄P₄O₁₀ in the crystalline state has a chair form with C₂ symmetry. However, the anion structure in aqueous solutions approaches a planar arrangement with the D_2h symmetry.     

ChemInform Abstract: Study of the Geometrical Structure and the Vibrational Spectra of P4O8, P4O6S2, and P4O6Se2.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

P6Se12]4-: a phosphorus-rich selenophosphate with low-valent P centers

The new selenophosphate Rb4P6Se12 features the trans-decalin-like, [P6Se12]4- anion, a phosphorus-rich species that possesses three parallel P-P bonds and formally P2+ and P4+ centers. The synthesis of Rb4P6Se12 was accomplished with the reductive addition of P to RbPSe6 and represents an interesting example of how alkali chalcophosphates can serve as starting materials to produce new compounds under mild reaction conditions.     

Synthese und Kristallstruktur von Rb8[P4N6(NH)4](NH2)2 mit dem adamantanartigen Anion [P4N6(NH)4]6−

Synthesis and Crystal Structure of Rb₈[P₄N₆(NH)₄](NH₂)₂ with the Adamantane-like Anion [P₄N₆(NH)₄]^6? RbNH₂ reacts with P₃N₅ (molar ratio 6:1) at 400°C within 5 d to colourless Rb₈[P₄N₆(NH)₄](NH₂)₂. Suitable crystals for a X-ray structure determination were obtained: The compound contains adamantane-like molecular anions [P₄N₆(NH)₄]^6?. Their centres of gravity are arranged in a distorted hexagonal primitive array. All trigonal prisms of this array contain one amide ion. Rubidium ions connect the anions irregularly.     

Hochdrucksynthese von BaSr2P6N12 und BaCa2P6N12 und Strukturvergleich der Reihe BaP2N4, BaCa2P6N12 und BaSr2P6N12

High‐Pressure Synthesis of BaSr₂P₆N₁₂ and BaCa₂P₆N₁₂ and Comparison of the Structures of BaP₂N₄, BaCa₂P₆N₁₂, and BaSr₂P₆N₁₂ The novel nitridophosphates BaCa₂P₆N₁₂ and BaSr₂P₆ N₁₂ were obtained by means of high‐pressure high‐temperature synthesis utilizing the multianvil technique (1200 °C, 5 GPa). The complex anion [PN₂^?] of the title compound is formally isoelectronic with silica. The crystal structure was solved from powder data and refined by the Rietveld method (BaCa₂P₆N₁₂: , Z = 4, a = 9,9578(2) Å; BaSr₂P₆N₁₂: , Z = 4, 10,0705(2) Å). The crystal structures are derived from that of BaP₂N₄ which is isotypic with a high pressure phase of CaB₂O₄ and BaGa₂S₄. For each compound the ³¹P solid state NMR spectrum yielded a single resonance (BaCa₂P₆N₁₂: 7.4 ppm; BaSr₂P₆N₁₂:3.9 ppm).     

Neue Rhodiumverbindungen mit LiCo6P4‐Struktur

New Rhodium Compounds with the LiCo₆P₄ Type Structure Five new phosphides and arsenides respectively of the formula ARh₆X₄ (A: Mg–Sr, Yb; X: P, As) were prepared by heating mixtures of the elements and investigated by means of single crystal X‐ray methods. They are isotypic and crystallize in the LiCo₆P₄ type structure (P6m2; Z = 1) (lattice constants see ”︁Inhaltsübersicht”︁”︁). The compounds belong to the large family of phosphides and arsenides, which have a metal : non‐metal ratio of about 2 : 1. Their structures are characterized by the environment of phosphorus and arsenic respectively, which is composed of trigonal prisms of metal atoms with additional metal atoms capping the rectangular faces of the prisms.