Hydrogen sulfide (H2S) has gained significant interest within the scientific community due to its expanding roles in different (patho)physiological processes. Despite this importance, the chemical mechanisms by which H2S exerts its action remain under-scrutinized. Biomimetic investigations in organic solution offer the potential to clarify these mechanisms and to delineate the differential reactivity between H2S and HS(-). However, such studies are hampered by the lack of readily-available sources of HS(-) that are soluble in organic solution. Here we present a simple method for preparing analytically pure tetrabutylammonium hydrosulfide (NBu4SH), which we anticipate will be of significant utility to researchers in the H2S and anion-binding communities.

The chemistry of several iron(III) porphyrinates containing silylthiolate ligands is described. The complexes are prepared by protonolysis reactions of silanethiols with the iron(III) precursors, [Fe(OMe)(TPP)] and [Fe(OH)(H2O)(TMP)] (TPP = dianion of meso-tetraphenylporphine; TMP = dianion of meso-tetramesitylporphine). Each of the compounds has been fully characterized in solution and the solid state. The stability of the silylthiolate complexes versus other iron(III) porphyrinate complexes containing sulfur-based ligands allows for an examination of their reactivity with several biologically relevant small molecules including H2S, NO, and 1-methylimidazole. Electrochemically, the silylthiolate complexes display a quasi-reversible one-electron oxidation event at potentials higher than that observed for an analogous arylthiolate complex. The behavior of these complexes versus other sulfur-ligated iron(III) porphyrinates is discussed.

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New measurement and assessment techniques have been applied to the radiochemical reevaluation of the Trinity Event. Thirteen trinitite samples were dissolved and analyzed using a combination of traditional decay counting methods and the mass spectrometry techniques. The resulting data were assessed using advanced simulation tools to afford a final yield determination of 24.8 ± 2 kilotons TNT equivalent, substantially higher than the previous DOE released value of 21 kilotons. This article is intended to complement the work of Susan Hanson and Warren Oldham, seen elsewhere in this issue. 1