Leveraging ligand-based proton and electron transfer for aerobic reactivity and catalysis.

While O is an abundant, benign, and thermodynamically potent oxidant, it is also kinetically inert. This frequently limits its use in synthetic transformations. Correspondingly, direct aerobic reactivity with O often requires comparatively harsh or forcing conditions to overcome this kinetic barrier.

Heavy chalcogenide-transition metal clusters as coordination polymer nodes.

While metal-oxygen clusters are widely used as secondary building units in the construction of coordination polymers or metal-organic frameworks, multimetallic nodes with heavier chalcogenide atoms (S, Se, and Te) are comparatively untapped. The lower electronegativity of heavy chalcogenides means that transition metal clusters of these elements generally exhibit enhanced coupling, delocalization, and redox-flexibility. Leveraging these features in coordination polymers provides these materials with extraordinary properties in catalysis, conductivity, magnetism, and photoactivity.

Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds.

Here we report that capping the molecule TTFtt (TTFtt = tetrathiafulvalene-2,3,6,7-tetrathiolate) with dialkyl tin groups enables the isolation of a stable series of redox congeners and facile transmetalation to Ni and Pd. TTFtt has been proposed as an attractive building block for molecular materials for two decades as it combines the redox chemistry of TTF and dithiolene units. TTFttH, however, is inherently unstable and the incorporation of TTFtt units into complexes or materials typically proceeds through the generation of the tetraanion TTFtt.