Controlling selectivity for dechlorination of poly(vinyl chloride) with (xantphos)RhCl.

Reaction of poly(vinyl chloride) (PVC) with 5 equiv. of triethyl silane in THF, in the presence of generated (xantphos)RhCl catalyst, results in partial reduction of PVC hydrodechlorination to yield poly(vinyl chloride--ethylene). Increasing catalyst loading or using ,-dimethylacetamide (DMA) as a solvent both diminished selectivity for hydrodechlorination, promoting competitive dehydrochlorination reactions. Reaction of PVC with 2 equiv. of sodium formate in THF in the presence of (xantphos)RhCl affords excellent selectivity for hydrodechlorination along with complete PVC dechlorination, yielding polyethylene-like polymers. Higher catalyst loadings were necessary to activate PVC towards reduction in this case. In contrast, reaction of PVC with 1 equiv. of NaH in DMA, in the presence of (xantphos)RhCl, exhibited good selectivity for dehydrochlorination, as well as much higher reaction rates. These results combined shed light on the interplay between critical reaction parameters that control PVC's mode of reactivity.