S/N crosstalk species derived from the interconnected reactivity of H₂ S and NO facilitate the transport of reactive sulfur and nitrogen species in signaling, transport, and regulatory processes. We report here that simple Fe²⁺ ions, such as those that are bioavailable in the labile iron pool (LIP), react with thionitrite (SNO^- ) and perthionitrite (SSNO^- ) to yield the dinitrosyl iron complex [Fe(NO)₂ (S₅ )]^- . In the reaction of FeCl₂ with SNO^- we were able to isolate the unstable intermediate hydrosulfido mononitrosyl iron complex [FeCl₂ (NO)(SH)]^- , which was characterized by X-ray crystallography. We also show that [Fe(NO)₂ (S₅ )]^- is a simple synthon for nitrosylated Fe-S clusters via its reduction with PPh₃ to yield Roussin's Red Salt ([Fe₂ S₂ (NO)₄ ]^2- ), which highlights the role of S/N crosstalk species in the assembly of fundamental Fe-S motifs.

Alkyltin clusters are exploited in nanolithography for the fabrication of microelectronics. The alkyltin Keggin family is unique among Keggin clusters across the periodic table; its members appear to favor the lower-symmetry β and γ isomers rather than the highly symmetrical α and ε isomers. Therefore, the alkyltin Keggin family may provide important fundamental information about the formation and isomerization of Keggin clusters. We have synthesized and structurally characterized a new butyltin Keggin cluster with a tetrahedral Ca²⁺ center, fully formulated [(BuSn)₁₂(CaO₄)(OCH₃)₁₂(O)₄(OH)₈]²⁺ (β-CaSn₁₂). The synthesis is a simple one-step process. Extensive solution characterization including electrospray ionization mass spectrometry, small-angle X-ray scattering, and multinuclear (¹H, ¹³C, and ¹¹⁹Sn) nuclear magnetic resonance shows β-CaSn₁₂ is essentially phase-pure and stable. This differs from the previously reported Na-centered analogues that always form a mixture of β and γ isomers, with facile interconversion. Therefore, this study has clarified prior confusion over complex spectroscopic and crystallographic characterization of the Na-centered analogues. Density functional theory calculations showed the following stability order: γ-CaSn₁₂ < γ-NaSn₁₂ < β-CaSn₁₂ < β-NaSn₁₂. The β analogue is always more stable than the γ analogue, consistent with experiment. Notable outcomes of this study include a rare tetrahedral Ca coordination, a Na-free alkyltin cluster (important for microelectronics manufacturing), and a better understanding of Keggin families built of different metal cations.

Large aqueous ions are interesting because they are useful in materials science (for example to generate thin films) but also because they serve as molecular models for the oxide-aqueous mineral interface where spectroscopy is difficult. Here we show that new clusters of the type M[(μ-OH)₂ Co(NH₃ )₄ ]₃ (NO₃ )₆ (M=Al, Ga) can be synthesized using Werner's century-old cluster as a substitutable framework. We substituted Group 13 metals into the hexol Co[(μ-OH)₂ Co(NH₃ )₄ ]₃⁶⁺ ion to make diamagnetic heterometallic ions. The solid-state structure of the hexol-type derivatives were determined by single-crystal XRD and NMR spectroscopy and confirmed that the solid-state structure persists in solution after dissolution into either D₂ O or [D₆ ]DMSO. Other compositions besides these diamagnetic ions can undoubtedly be made using a similar approach, which considerably expands the number of stable aqueous heteronuclear ions.

Hydrogen sulfide (H2 S) has emerged as a crucial biomolecule in physiology and cellular signaling. Key challenges associated with developing new chemical tools for understanding the biological roles of H2 S include developing platforms that enable reversible binding of this important biomolecule. The first synthetic small molecule receptor for the hydrosulfide anion, HS(-) , using only reversible, hydrogen-bonding interactions in a series of bis(ethynylaniline) derivatives, is reported. Binding constants of up to 90 300±8700 m(-1) were obtained in MeCN. The fundamental science of reversible sulfide binding, in this case featuring a key CH⋅⋅⋅S hydrogen bond, will expand the possibility for discovery of sulfide protein targets and molecular recognition agents.