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We show in this work how lithium tellurolate Li(X)_nTeCH₂SiMe₃(X = THF,n= 1, 1; X = 12-crown-4,n= 2, 2), can serve as an effective Te-atom transfer reagent to all group 5 transition metal halide precursors irrespective of their oxidation state.

 

Multicopper active sites for small molecule activation in materials and enzymatic systems rely on controlled but adaptable coordination spheres about copper clusters for enabling challenging chemical transformations. To translate this constrained flexibility into molecular multicopper complexes, developments are needed in both ligand design for clusters and synthetic strategies for modifying the cluster cores. The present study investigates the chemistry of a class of pyridyldiimine-derived macrocycles with geometrically flexible aliphatic linkers of varying lengths (nPDI2, n = 2, 3). A series of dicopper complexes bound by the nPDI2 ligands are described and found to exhibit improved solubility over their parent analogs due to the incorporation of 4-tBu groups on the pyridyl units and the use of triflate counterions. The ensuing synthetic study investigated methods for introducing various bridging ligands (µ-X; X = F, Cl, Br, N3, NO2, OSiMe3, OH, OTf) between the two copper centers within the macrocycle-supported complexes. Traditional anion metathesis routes were unsuccessful, but the abstraction of bridging halides resulted in “open-core” complexes suitable for capturing various anions. The geometric flexibility of the nPDI2 macrocycles was reflected in the various solid-state geometries, Cu–Cu distances, and relative Cu coordination spheres on variation in the identity of the captured anion.

 

A series of mono‐ and di‐nuclear Ag^Icomplexes supported by a flexible macrocyclic ligand are reported. The geometric flexibility of the ligand was found to allow for a range of Ag−Ag interactions in the disilver complexes, depending on the identities of both the ancillary ligand and the counterion. Studies of the solution‐phase dynamic exchange processes for these latter complexes found rapid interconversion through a mechanism that retained the multi‐nuclearity. Quantum Theory of Atoms in Molecules (QTAIM) and Independent Gradient Model based on Hirshfeld partition (IGMH) analyses are used to evaluate the d¹⁰‐d¹⁰interactions between silver centers in the various geometries observed for the solid‐state structures of these complexes, revealing nearly identical Ag−Ag interactions, regardless of the relative geometries of the Ag centers. Instead, a weak, but non‐negligible, inter‐ligand interaction between two isocyanide units may contribute to the folded‐ligand geometry observed in the solid state.

 

The separation and purification of niobium and tantalum, which co-occur in natural sources, is difficult due to their similar physical and chemical properties. The current industrial method for separating Ta/Nb mixtures uses an energy-intensive process with caustic and toxic conditions. It is of interest to develop alternative, fundamental methodologies for the purification of these technologically important metals that improve upon their environmental impact. Herein, we introduce new Ta/Nb imido compounds: M( t BuN)(TriNOx) (1-M) bound by the TriNOx 3− ligand and demonstrate a fundamental, proof-of-concept Ta/Nb separation based on differences in the imido reactivities. Despite the nearly identical structures of 1-M, density functional theory (DFT)-computed electronic structures of 1-M indicate enhanced basic character of the imido group in 1-Ta as compared to 1-Nb. Accordingly, the rate of CO 2 insertion into the MN imido bond of 1-Ta to form a carbamate complex (2-Ta) was selective compared to the analogous, unobserved reaction with 1-Nb. Differences in solubility between the imido and carbamate complexes allowed for separation of the carbamate complex, and led to an efficient Ta/Nb separation ( S Ta/Nb = 404 ± 150) dependent on the kinetic differences in nucleophilicities between the imido moieties in 1-Ta and 1-Nb.