Spirobifluorene-based Porous Organic Polymers as Efficient Porous Supports for Pd and Pt for Selective Hydrogenation

Spirobifluorene-based porous organic polymers (POP) were synthesized following two different protocols; the acetylenic coupling reaction conditions and the Sonogashira cross-coupling reaction. These were utilized as support for the hydrogenation of a series of species containing unsaturated C=C and C=O bonds (4-nitrostyrene, 4-bromobenzophenone, acetophenone, 7-nitro-1-tetralone and 1,2-naphtoquinone confirmed their efficiency). POP1 prepared via a copper-catalysis protocol was completely inactive, while POP2-4 containing residual Pd exhibited different activities in accordance to the accessibility of the substrates to the metal. Further deposition of 0.5wt% Pd led to active and stable catalysts. They were easily separated by filtration, and after re-dispersion, afforded the same performances for ten successive cycles. This study also evidenced the specific role of the support in these reactions by comparing the behavior of Pd/POP with that of a Pd/C catalyst with the same loading of palladium. The deposition of Pt on these supports led to sub-nanometric particles and, in accordance, to a different catalytic behavior reflected merely by differences in the selectivity.