Matrix isolation study of the reaction of diborane with hydrogen sulfide: spectroscopic characterization of mercaptoborane, H2BSH

Abstract

Merged jet copyrolysis of mixtures of Ar/BzH6 and Ar/HzS followed by trapping in a cryogenic matrix has led to the formation, isolation, and characterization of mercaptoborane, H2BSH. Eight of the nine fundamentals of this molecule were observed, including the boron-sulfur stretching mode at 804 cm-l ("B). Local density functional and normal-coordinate calculations were carried out to assist in assigning the observed fundamentals. The position of B-S stretching mode, compared to a range of known compounds, suggests single bond character for the B-S bond. Additional products were observed, including HBS, and suggests further reaction of HzBSH at high temperatures. A mechanism for the reaction is proposed.

The Reactivity of Mercapto Groups against Boron Hydrides in Pincer Ligated Nickel Mercapto Complexes

“…We believed that complex 1 a reacted with BH 3 ⋅THF to form 1 aa and HSBH 2 ⋅THF first; then 1 aa further reacted with BH 3 ⋅THF to form 1 ab (Scheme ). The mercaptoborane species HSBH 2 was previously observed and characterized by Ault and co‐workers through matrix isolation techniques, and its THF adduct HSBH 2 ⋅THF was previously reported by Binder and co‐workers as an unstable and highly reactive species …”

Identification of diborane(4) with bridging B–H–B bonds

“…[16][17][18][19][20] Investigations of transient boron species using the matrixisolation technique have been reported. [21][22][23][24][25] For instance, reactions of H 2 with boron atoms evaporated with a pulsed laser and condensed in excess argon at 10 K yielded products such as BH, (H 2 )(BH) complex, BH 3 , (H 2 )(BH 3 ) complex, HBBH and B 2 H 6 , identied from infrared absorption spectra. 23 The irradiation of samples of B 2 H 6 diluted in neon or argon at 4 K with light at 16.8 eV followed by X-rays and electrons at 50 eV enabled the detection of BH 2 , BO, B 2 and HBBH through electron-paramagnetic-resonance spectra, 24 but no neutral boron hydride species with less than six H atoms and a bridging B-H-B bond has been experimentally identied before our work.…”

M–S Multiple Bond in HMSH, H2MS, and HMS Molecules (M = B, Al, Ga): Matrix Infrared Spectra and Theoretical Calculations

“…Group C absorptions at 2738.9 and 1202.2 cm −1 appeared after codeposition and sharply increased on full-arc mercury lamp photolysis, which were assigned to HBS in the previous work and we agree the assignment. 21,22 In addition, the known BO 2 absorption at 1323 cm −1 was observed after sample deposition and the absorptions due to H 2 O and CO 2 (not shown in figures) can only be decreased at most but never be eliminated.…”