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1. Efficient Production of Carbonyl Sulfide in the Low‐NO _x Oxidation of Dimethyl Sulfide

   https://doi.org/10.1029/2021GL096838  

   Jernigan, Christopher M.; Fite, Charles H.; Vereecken, Luc; Berkelhammer, Max B.; Rollins, Andrew W.; Rickly, Pamela S.; Novelli, Anna; Taraborrelli, Domenico; Holmes, Christopher D.; Bertram, Timothy H. (January 2022, Geophysical Research Letters)

   Abstract The oxidation of carbonyl sulfide (OCS) is the primary, continuous source of stratospheric sulfate aerosol particles, which can scatter shortwave radiation and catalyze heterogeneous reactions in the stratosphere. While it has been estimated that the oxidation of dimethyl sulfide (DMS), emitted from the surface ocean accounts for 8%–20% of the global OCS source, there is no existing DMS oxidation mechanism relevant to the marine atmosphere that is consistent with an OCS source of this magnitude. We describe new laboratory measurements and theoretical analyses of DMS oxidation that provide a mechanistic description for OCS production from hydroperoxymethyl thioformate, a ubiquitous, soluble DMS oxidation product. We incorporate this chemical mechanism into a global chemical transport model, showing that OCS production from DMS is a factor of 3 smaller than current estimates, displays a maximum in the tropics consistent with field observations and is sensitive to multiphase cloud chemistry. 

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2. Colorimetric Carbonyl Sulfide (COS)/Hydrogen Sulfide (H ₂ S) Donation from γ‐Ketothiocarbamate Donor Motifs

   https://doi.org/10.1002/anie.201806854  

   Zhao, Yu; Steiger, Andrea K.; Pluth, Michael D. (September 2018, Angewandte Chemie International Edition)

   Abstract Hydrogen sulfide (H₂S) is a biologically active molecule that exhibits protective effects in a variety of physiological and pathological processes. Although several H₂S‐related biological effects have been discovered by using H₂S donors, knowing how much H₂S has been released from donors under different conditions remains challenging. Now, a series of γ‐ketothiocarbamate (γ‐KetoTCM) compounds that provide the first examples of colorimetric H₂S donors and enable direct quantification of H₂S release, were reported. These compounds are activated through a pH‐dependent deprotonation/β‐elimination sequence to release carbonyl sulfide (COS), which is quickly converted into H₂S by carbonic anhydrase. Thep‐nitroaniline released upon donor activation provides an optical readout that correlates directly to COS/H₂S release, thus enabling colorimetric measurement of H₂S donation. 

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3. [Ni ₃₀ S ₁₆ (PEt ₃ ) ₁₁ ]: an open-shell nickel sulfide nanocluster with a “metal-like” core

   https://doi.org/10.1039/D2SC00960A  

   Touchton, Alexander J.; Wu, Guang; Hayton, Trevor W. (May 2022, Chemical Science)

   Reaction of [Ni(1,5-cod) 2 ] (30 equiv.) with PEt 3 (46 equiv.) and S 8 (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni 30 S 16 (PEt 3 ) 11 ] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact “metal-like” core indicative of a high degree of Ni–Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO–LUMO gap. In situ monitoring by ESI-MS and 31 P{ 1 H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni 8 S 5 (PEt 3 ) 7 ] and [Ni 26 S 14 (PEt 3 ) 10 ] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal–metal bonding are isolable for nickel, and not just the noble metals. 

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4. Chemical dynamics study on the gas-phase reaction of the D1-silylidyne radical (SiD; X ² Π) with deuterium sulfide (D ₂ S) and hydrogen sulfide (H ₂ S)

   https://doi.org/10.1039/d1cp01629f  

   Goettl, Shane J.; Doddipatla, Srinivas; Yang, Zhenghai; He, Chao; Kaiser, Ralf I.; Silva, Mateus X.; Galvão, Breno R.; Millar, Tom J. (June 2021, Physical Chemistry Chemical Physics)

   The reactions of the D1-silylidyne radical (SiD; X 2 Π) with deuterium sulfide (D 2 S; X 1 A 1 ) and hydrogen sulfide (H 2 S; X 1 A 1 ) were conducted utilizing a crossed molecular beams machine under single collision conditions. The experimental work was carried out in conjunction with electronic structure calculations. The elementary reaction commences with a barrierless addition of the D1-silylidyne radical to one of the non-bonding electron pairs of the sulfur atom of hydrogen (deuterium) sulfide followed by possible bond rotation isomerization and multiple atomic hydrogen (deuterium) migrations. Unimolecular decomposition of the reaction intermediates lead eventually to the D1-thiosilaformyl radical (DSiS) (p1) and D2-silanethione (D 2 SiS) (p3) via molecular and atomic deuterium loss channels (SiD–D 2 S system) along with the D1-thiosilaformyl radical (DSiS) (p1) and D1-silanethione (HDSiS) (p3) through molecular and atomic hydrogen ejection (SiD–H 2 S system) via indirect scattering dynamics in barrierless and overall exoergic reactions. Our study provides a look into the complex dynamics of the silicon and sulfur chemistries involving multiple deuterium/hydrogen shifts and tight exit transition states, as well as insight into silicon- and sulfur-containing molecule formation pathways in deep space. Although neither of the non-deuterated species – the thiosilaformyl radical (HSiS) and silanethione (H 2 SiS) – have been observed in the interstellar medium (ISM) thus far, astrochemical models presented here predict relative abundances in the Orion Kleinmann-Low nebula to be sufficiently high enough for detection. 

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5. Anchoring the hydrogen sulfide dimer potential energy surface to juxtapose (H ₂ S) ₂ with (H ₂ O) ₂

   https://doi.org/10.1063/5.0008929  

   Perkins, Morgan A.; Barlow, Kayleigh R.; Dreux, Katelyn M.; Tschumper, Gregory S. (June 2020, The Journal of Chemical Physics)