Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Siewert, Birgit; Müller, Ulrich

doi:10.1002/zaac.19926090315

Cited by 13 publications

(2 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Molecular dimensions and conformation are within standard uncertainties the same for the molecules in the two polymorphs. These are also very similar to those observed in the tetrakis(tris(μ 2 -sulfido)-tetra-arsenic)-tetraphenylphosphonium chloride complex (Siewert and Müller, 1992) where the As–As bonds are in the range 2.464(3)–2.494(3) Å and the As–S bonds in the range 2.229(6)–2.243(6) Å. For paradimorphite, the As–As bonds of the triangular base are in the range 2.4673(4)–2.4855(6) Å and are on average significantly shorter than those observed for the As 4 S 4 molecules in realgar (2.566(1)–2.571(1) Å), bonazziite (2.579(1) Å), pararealgar (2.484(4)–2.534(4) Å) and alacránite (2.579(5) Å), and those in the As 4 S 5 molecules in uzonite (2.527(1) Å) and alacránite (2.566(6) Å).…”

Section: Description Of the Crystal Structure And Discussionsupporting

confidence: 85%

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Campostrini

Castellano

Demartin

et al. 2022

MinMag

View full text Add to dashboard Cite

The new mineral paradimorphite corresponds to the high temperature polymorph of As4S3, whose existence was supposed by Arcangelo Scacchi in 1850 in the fumaroles at the Solfatara di Pozzuoli, Campi Flegrei, near Napoli, Italy. Crystals of paradimorphite are orange yellow, transparent or semitransparent, with adamantine lustre. Habit is prismatic and observed forms are {110}, {101}, {111}, {100}, {010} and {001}. Tenacity is brittle, no distinct cleavage is observed and fracture is conchoidal. The mineral does not fluoresce in long- or shortwave ultraviolet light. No twinning is apparent. The streak is saffron yellow. Hardness (Mohs) = 1–2. The observed density is 3.510(3) g/cm3, calculated density is 3.500 g/cm3. The mineral is orthorhombic, space group Pnma, with a = 9.1577(7), b = 8.0332(6), c = 10.2005(8) Å, V = 750.41(10) Å3 and Z = 4. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 6.299(48)(011), 5.186(100)(111), 4.174(31)(201), 3.133(34)(022), 3.116(58)(212), 2.980(41)(122), 1.846 (27)(413) and 1.808(23)(134). The structure was refined to R = 0.0229 for 979 reflections with I >2σ(I). Crystals of paradimorphite contain As4S3 molecules, of idealised C3v symmetry, with the four arsenic atoms in a triangular pyramidal arrangement, with sulfur atom bridges on the three adjacent apical edges. Molecular dimensions and conformation are identical within standard uncertainties with those of the low-temperature polymorph dimorphite. No substantial differences, neither in the molecular packing nor in the molecular orientation, could be observed; minor differences being related to intermolecular distances only.

show abstract

Section: Description Of the Crystal Structure And Discussionsupporting

confidence: 85%

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Campostrini

Castellano

Demartin

et al. 2022

MinMag

View full text Add to dashboard Cite

show abstract

“…Such species can be found for the transition metal (V, Nb, Mo, W, Re) square pyramidal oxohalido anions . Most of them contain either pyridine (Py), , tetrahydrofuran (THF), − acetonitrile (CH 3 CN), − or water as ligands due to their use as solvents in reactions. The ligand can therefore have access to the sixth coordination site and form a distorted octahedron around the metal center in the anion.…”

Section: Introductionmentioning

confidence: 99%

Coordination of a Neutral Ligand to a Metal Center of Oxohalido Anions: Fact or Fiction?

et al. 2021

View full text Add to dashboard Cite

Can a neutral ligand bond to a metal center of a square pyramidal oxohalido anion at the available sixth octahedral position? Crystal structures of some compounds indeed suggest that ligands, such as THF, pyridine, H 2 O, NH 3 , and CH 3 CN, can interact with the central metal atom, because they are oriented with their heteroatom toward the metal center with distances being within the bonding range. However, this assumption that is based on chemical intuition is wrong. In-depth analysis of interactions between ligands and oxohalido anions (e.g., VOX 4 – , NbOCl 4 – ) reveals that the bonding of a neutral ligand is almost entirely due to electrostatic interactions between the H atoms of a ligand and halido atoms of an anion. Furthermore, ab initio calculations indicate that the ligand–VOF 4 – interactions represent only about one-quarter of the total binding of the ligand within the crystal structure, whereas the remaining binding is due to crystal packing effects. The current study therefore shows that relying solely on the structural aspects of solved crystal structures, such as ligand orientation and bond distances, can lead to the wrong interpretation of the chemical bonding.

show abstract

Tellurium Polycations by Oxidation of Tellurium with Tungsten Halides Syntheses and Crystal Structures of Te₆(WOCl₄)₂ and Te₆I₂(WCl₆)₂

Beck

1995

Chem. Ber.

View full text Add to dashboard Cite

The oxidation of tellurium by transition-metal halides is a useful synthetic route to new tellurium polycations['l. Tungsten halides turn out as selective oxidants towards tellurium, which makes the synthesis of polycations possible that cannot be obtained by the classical oxidation with AsF5/SbF5 in liquid SO2I21, e.g. TegtF3l or [Te$'], [4,5]. Two further specific reactions of tungsten halides are now presented. The reaction of WOC4 with tellurium leads to the often but never confirmed polycation Tef', and from WC16, I2 and tellurium Te& can be obtained, which is isostructural with the selenium analogue Se611+ [9]. Preparation and Properties of Te6(WOC14)2 and Te612(WCb)2Elemental tellurium is selectivly oxidized by WOC14 at 210-230°C to Tef+, WOC14 is reduced to WOCl,.The reaction is carried out in a sealed, evacuated glass ampoule, Te6(W0C1& is obtained in the colder part of the ampoule in nearly quantitative yield as black, lustrous, predominantly needle-shaped crystals which are slowly hydrolyzed in air. If any part of the ampoule is allowed to become colder than 190°C, crystalline WOCl, deposits and Te6(WOC14)2 will decompose completely into tellurium and WOC,. Also at temperatures higher than 230°C Te6(WOC14)2 decomposes into elemental tellurium and molten WOC,. The temperature range of stability is limited to 190-230°C. The magnetic properties have been studied in the temperature range from 20 to 300 K by means of a SQUID magnetometer. Te6(WOC14)2 is paramagnetic, the reciprocal susceptibility increases linearly with temperature with a Curie-Weiss constant 0 = -17 K. The magnetic moment amounts to 1.15 B.M. for the smallest formula unit Te3W0Cl4, slightly less than the expected value of 1.73 B.M. for one unpaired electron.Te612(WC16)2 is obtained from tellurium, iodine andThe reaction is carried out in a sealed glass ampoule under Ar. At 300°C the components are molten to a black liquid, which on cooling forms a black amorphous mass. Annealing at 150°C yields Te6I2(wcl6), in quantitative yield. To prevent the decomposition into the different volatile starting compounds Te, I2 and WC16 it is essential to minimize the temperature gradient along the ampoule. Under these conditions, the content of the ampoule crystallizes within three months as black plate-like moisture-sensitive crystals that can reach.5 X 5 X 1 mm in size.

show abstract

Die Bildung von PPh₄[WOCl₄ · THF] und PPh₄Cl · 4As₄S₃ aus W(CO)₆ und PPh₄[As₂SCl₅] sowie ihre Kristallstrukturen

Cited by 13 publications

References 15 publications

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Coordination of a Neutral Ligand to a Metal Center of Oxohalido Anions: Fact or Fiction?

Tellurium Polycations by Oxidation of Tellurium with Tungsten Halides Syntheses and Crystal Structures of Te₆(WOCl₄)₂ and Te₆I₂(WCl₆)₂

Contact Info

Product

Resources

About

Die Bildung von PPh4[WOCl4 · THF] und PPh4Cl · 4As4S3 aus W(CO)6 und PPh4[As2SCl5] sowie ihre Kristallstrukturen

Cited by 13 publications

References 15 publications

Paradimorphite, β-As4S3, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Paradimorphite, β-As4S3, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Coordination of a Neutral Ligand to a Metal Center of Oxohalido Anions: Fact or Fiction?

Tellurium Polycations by Oxidation of Tellurium with Tungsten Halides Syntheses and Crystal Structures of Te6(WOCl4)2 and Te6I2(WCl6)2

Contact Info

Product

Resources

About

Die Bildung von PPh₄[WOCl₄ · THF] und PPh₄Cl · 4As₄S₃ aus W(CO)₆ und PPh₄[As₂SCl₅] sowie ihre Kristallstrukturen

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Paradimorphite, β-As₄S₃, a vintage new mineral from Solfatara di Pozzuoli and Vesuvius, Napoli, Italy

Tellurium Polycations by Oxidation of Tellurium with Tungsten Halides Syntheses and Crystal Structures of Te₆(WOCl₄)₂ and Te₆I₂(WCl₆)₂