Using a dual catalysis approach, epoxide/lactone copolymers were synthesized with control over tacticity, molecular weight, crystallinity, and comonomer content.

Reductive elimination (RE) is a critical step in many catalytic processes. The reductive elimination of unsaturated groups (aryl, vinyl and ethynyl) from Pd(II) species is considerably faster than RE of saturated alkyl groups. Pd(II) dimethyl complexes ligated by chelating diimine ligands are stable toward RE unless subjected to a thermal or redox stimulus. Herein, we report the spontaneous RE of ethane from (azpy)PdMe complexes and the unique role of the redox-active azopyridine (azpy) ligands in facilitating this reaction. The (azpy)PdMe complexes are air- and moisture-stable in the solid form, but they readily produce ethane upon dissolution in polar solvents at temperatures from 10 °C to room temperature without the need for an external oxidant or elevated temperatures. Experimental and computational studies indicate that a bimolecular methyl transfer precedes the reductive elimination step, where both steps are facilitated by the redox-active azopyridine ligand.

Reduction of the insulating one-dimensional coordination polymer [Cu(abpy)PF 6 ] n , 1a(PF 6 ), (abpy = 2,2'-azobispyridine) yields the conductive,p orous polymer [Cu-(abpy)] n , 2a. Pressed pellets of neutral 2a exhibit aconductivity of 0.093 Scm À1 at room temperature and aB runauer-Emmett-Teller (BET) surface area of 56 m 2 g À1 .Fine powders of 2a have aB ET surface area of 90 m 2 g À1 .C yclic voltammetry shows that the reduction of 1a(PF 6 )t o2a is quasireversible,indicative of facile charge transfer through the bulk material. The BET surface area of the reduced polymer 2 can be controlled by changing the size of the counteranion Xinthe cationic [Cu(abpy)X] n .R eduction of [Cu(abpy)X] n with X = Br (2b)orB Ar F (2c;B Ar F = tetrakis(3,5-bis(trifluoromethyl)phenyl)), affords [Cu(abpy)] n polymers with surface areas of 60 and 200 m 2 g À1 ,respectively.