Solvent screening is pivotal in the optimization of reaction conditions for metal-catalyzed reactions. However, to date little is known about the role of solvent effects in driving in situ structural evolution of metal-containing species towards polynuclear organometallic cluster intermediates and determining their reactivity. We herein isolate two distinct thirteen-membered silver cluster isomers, Ag13-A and Ag13-M, in acetone and methanol, respectively.

Since the concept of aromaticity was first introduced in transition metal complexes, metals have become a crucial component for modulating aromaticity, leading to a variety of structural frameworks. Initial studies successfully achieved aromatic pentalene dianions through metal-ion coordination, and recent advancements in bridgehead metallapentalenes have demonstrated the transformation of antiaromaticity into aromaticity.

We report on the utilization of the ethylene-bridged bis[(dialkylamino)cyclopropenimine] (bisCPI) ligand, LCPI, to give access to new main-group E(II) halide complexes (E = Ge, Sn, Pb; 1, 2, 3). Subsequent reduction with Collman's reagent (Na2Fe(CO)4 • dioxane) enables the isolation of a series of zero-valent tetrylone-tetracarbonyl iron complexes, (LCPI)E(Fe(CO)4 (E = Ge (4), Sn (5), Pb (6)).

Nitroso compounds, R-N═O, containing N═O double bonds are ubiquitous and widely utilized in organic synthesis. In contrast, heavier congeners of nitroso compounds, namely pnictinidene chalcogenides R-Pn = E (Pn = P, As, Sb, Bi; E = O, S, Se, Te), are highly reactive and scarce. They have been stabilized in the coordination sphere of Lewis acid/base or by pronounced contribution from resonance structures, whereas free species with unperturbed pnictogen-chalcogen double bonds remains elusive.

Metallabenzyne has attracted considerable interest from theoreticians and experimentalists since its first isolation in 2001. However, metallasilabenzyne, formed by the replacement of the carbyne carbon with a silicon atom in metallabenzyne, has never been reported either theoretically or experimentally. Here we carry out density functional theory (DFT) calculations on this system for the first time. Our results reveal a polarized and weak Os–Si triple bond in osmasilabenzyne due to the reluctance of the silicon to participate in π bonding.