Synthesis of Square Planar Cu4 Clusters.

Template-assisted synthesis of well-defined polynuclear clusters remains a challenge for [M4 ] square planar topologies. Herein, we present a tetraamine scaffold R L(NH2 )4 , where L is a rigidified resorcin[4]arene, to direct the formation of C4 -symmetric R L(NH)4 Cu4 clusters with Cu-Cu distances around 2.7 Å, suggesting metal-metal direct interactions are operative since the sum of copper's van der Waals radii is 2.8 Å. DFT calculations display HOMO to HOMO-3 residing all within a 0.1 eV gap. These four orbitals display significant electron density contribution from the Cu centers suggesting a delocalized electronic structure. The one-electron oxidized [Cu4 ]+ species was probed by variable temperature X-band continuous wave-electron paramagnetic resonance (CW-EPR), which displays a multiline spectrum at room temperature. This work presents a novel synthetic strategy for [M4 ] clusters and a new platform to investigate activation of small molecules.

Reversible dioxygen uptake at [Cu4] clusters.

Dioxygen binding solely through non-covalent interactions is rare. In living systems, dioxygen transport takes place via iron or copper-containing biological cofactors. Specifically, a reversible covalent interaction is established when O2 binds to the mono or polynuclear metal center. However, O2 stabilization in the absence of covalent bond formation is challenging and rarely observed. Here, we demonstrate a unique example of reversible non-covalent binding of dioxygen within the cavity of a well-defined synthetic all-Cu(i) tetracopper cluster.

Density functional theory studies on the generation of trimethylenemethanes from the ring opening of dialkoxymethylenecyclopropanes and methylenecyclopropanethioacetals and follow-up reactions.

This work reports a detailed DFT study on the generation of trimethylenemethanes (TMMs) from the ring opening of dialkoxymethylenecyclopropane (DMCP), methylenecyclopropanethioacetal (MCPT), and substituted derivatives of DMCP and MCPT, as well as follow-up reactions of the TMMs. The singlet DMCP and MCPT were found to be 51.32 and 53.77 kcal mol-1 more stable than the triplet DMCP and MCPT respectively, corresponding to triplet:singlet population ratios of 1:1038 and 1:1040, respectively, at 25 °C using Boltzmann distribution, implying that the proportion of the triplet species is negligible at 25 °C. The ring-opening reactions occur through singlet transition states with barriers of 40.68 and 42.27 kcal mol-1 for DMCP and MCPT, respectively, and yield TMMs that are very unstable compared to the precursors, with the triplet TMM being far more stable than the singlet. Whereas the singlet TMMs readily undergo cycloaddition reactions with olefins to form five-membered carbocyclic rings, the triplet species do not. The selectivity of the reactions of the DMCP TMMs is very sensitive to temperature; at 25°C, cycloaddition with olefins and ring-closure to form ketenes have very comparable barriers while temperatures above 150 °C favor the exclusive formation of a ketene followed by dimerization. In MCPT, ring closure to form ketenes is the favored reaction at all temperatures studied. Pathways for the generation of trimethylenemethanes from their precursors and follow-up reactions.