High molecular weight boron sulfides. V. Vaporization behavior of the boron-sulfur system

Abstract

The vaporization behavior of the boron-sulfur system has been studied mass spectrometrically with a glassy, sulfur-rich B2S3 sample, a stoichiometric B2S3 sample, a stoichiometric B2S3 -Zn mixture, and a FeS-B-Zn mixture. Glassy B& gave the most intense and most complicated spectra; the stoichiometric BsS3 sample, the stoichiometric B2S3-Zn mixture, and the early stages of the FeS-B-Zn mixture gave, in the temperature range 400-650 O, indistinguishable spectra that were intermediate in intensity and complexity; and the ZnS-B system, to which the FeS-B-Zn mixture converted in later stages, gave the simplest spectra with the lowest intensities. Ion intensities, appearance potentials, metastable transitions, fragmentation patterns, and temperature dependences are used to show that the parent ions from stoichiometric BZS3 were polymers of B2S3(g) and that BZS3(s) vaporizes congruently. Sulfur-rich samples vaporize incongruently to give polymers of both BSz(g) and BzS3(g). Sulfurdeficient systems also give B2S2(g). Polysulfide bonds are suggested as the cause of the higher volatility and lower melting points of the sulfur-rich samples.he discovery of the gaseous ions of polymeric com-

In search of the smallest boroxol‐type heterocyclic ring system: Planar hexagonal B3S3+ cluster with double 6π/2σ aromaticity

“…Early mass spectroscopic studies suggested that the cationic B 2 S 2 + cluster may be a precursor for high molecular weight clusters 40 . It is valuable to calculate the formation energy of the D 3 h B 3 S 3 + ( 1 ) cluster using linear B 2 S 2 + and BS species as reactants, according to the following equation: B 2 S 2 + ( D ∞ h , 2 ∑ g ) + BS ( D ∞ h , 2 ∑ g ) = B 3 S 3 + ( 1 , D 3 h , 1 A 1 ′).…”

“…Selected literature on binary B m S n clusters is surveyed here. In the 1960s and 1970s, mass spectroscopic studies in the gas phase confirmed the existence of a series of boron sulfide cations, suggesting that BS 2 + , B 2 S 2 + , and B 2 S 3 + are important precursors to form high molecular weight B‐S clusters 37–41 . Quite recently, computational works from us revealed rhombic B 2 S 2 and pentagonal B 3 S 2 rings in B 4 S 4 and B 3 S 2 H 3 clusters, respectively 42–44 .…”

“…In the 1960s and 1970s, mass spectroscopic studies in the gas phase confirmed the existence of a series of boron sulfide cations, suggesting that BS 2 + , B 2 S 2 + , and B 2 S 3 + are important precursors to form high molecular weight B-S clusters. [37][38][39][40][41] Quite recently, computational works from us revealed rhombic B 2 S 2 and pentagonal B 3 S 2 rings in B 4 S 4 and B 3 S 2 H 3 clusters, respectively. [42][43][44] The D 2h B 6 S 6 0/−/2global minimum (GM) clusters 45 were found to contain fused twin B 3 S 2 rings with elongated overall shapes.…”

Structural and energetic exploration of a boron‐rich sulfide cluster B6S

“…Due to the close similarity between S (3s 2 3p 4 ) and O (2s 2 2p 4 ) in valence electron configuration, the boron‐sulfur clusters have also been the focus of research interests 47–62, though the related data is much less than those of B m O n . Small boron sulfide species BS 2 + , B 2 S 2 + , B 2 S 3 + were already characterized by gas phase spectroscopy studies more than 30 years ago 52–55. The di/tri‐anionic BS 3 3− , B 2 S 4 2− , B 2 S 5 2− , B 3 S 6 3− have been found to exist as building blocks in materials 56.…”

Preparation and characterization of B2S3-based chalcogenide glasses

“…Crystal structure for B2S3 as proposed by Chen(41). Crystal structure of BjSj showing four-and six-membered rings.…”