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Abstract Persulfides (RSS^–) and thioselenides (RSSe^–) play important roles in biological S and Se transfer reactions, and their interactions with Lewis acidic moieties exert control over reactivity. Here, we report the synthesis and reactivity of mononuclear Zn²⁺persulfide and thioselenide complexes from a unified synthetic strategy of using isolable dichalcogenide precursors. Highlighting the benefits of replacing S with Se, we use⁷⁷Se NMR spectroscopy to reveal the effects of Lewis acid coordination (K⁺, Na⁺, Zn²⁺) on the electronic environment of the terminal Se of the thioselenide (R–S_β–Se_α^–). Coordination of RSSe^–to Zn²⁺polarizes the Se─S bond, rendering the internal sulfur atom (R–S_β–Se_α^–) susceptible to nucleophilic attack and resulting in selenide (Se^2–) release. We also prepared a mononuclear Zn²⁺persulfide complex and probed differences in persulfide nucleophilicity when compared to the parent thiolate. Alkylation of the Zn²⁺persulfide is considerably faster than the Zn²⁺thiolate, supporting the proposed nucleophilicity enhancement of persulfides due to the α‐effect, and providing new insights into persulfide reactivity when coordinated to metals. Taken together, these investigations highlight the utility of small molecule synthetic models in advancing insights into the biological chemistry of metal dichaclogenides. 

Mechanistic differences in S/Se chemistry enable direct H₂Se release from selenocarbamates. 

Hydrogen selenide (H2Se) is an emerging bioregulator and precursor to essential selenium-containing biomolecules. We show that aryl isoselenocyanates (ISeC-R) release H2Se upon activation by cysteine, and that electronic substitution can modulate release profiles. We also demonstrate applications to live cell imaging, expanding available tools for investigating H2Se chemical biology. 

The [ Ph B( t BuIm) 3 ] 1− ligand has gained increased attention since it was first reported in 2006 due to its ability to stabilize highly reactive first row transition metal complexes. In this work, we investigate the coordination chemistry of this ligand with redox-inert zinc to understand how a zinc metal center behaves in such a strong coordinating environment. The Ph B( t BuIm) 3 ZnCl (1) complex can be formed via deprotonation of [ Ph B( t BuIm) 3 ][OTf] 2 followed by the addition of ZnCl 2 . Salt metathesis reaction with nucleophilic n -BuLi yields the highly carbon-rich zinc coordination complex Ph B( t BuIm) 3 ZnBu (2) with three carbene atom donors and one carbanion donor. In contrast, reaction of complex 1 with a less nucleophilic polysulfide reagent, [K.18-C-6] 2 [S 4 ], leads to the formation of a tetrahedral zinc tetrasulfido complex via protonation of one carbene donor to form Ph B( t BuIm) 2 ( t BuImH)Zn(κ 2 -S 4 ) (3).