Sequestration of ruthenium residues via efficient fluorous-enyne termination

Abstract

The creation of polymers without metal contamination remains a significant challenge for metathesis-based polymerization techniques and has complicated applications in biomedical and electronic applications. This communication reports a new approach for the removal of ruthenium byproducts through the design of an enyne terminator for metathesis polymerization that contains a fluorous tag. Upon reaction of a living polymer chain with the enyne, the ruthenium center is captured as a stable sulfur-chelated complex that can be efficiently removed after a single filtration through a fluorous cartridge. Levels of ruthenium residues as determined by ICP-MS were found to depend on the monomer structure, eluting solvent, and the degree of polymerization targeted. Ruthenium residues were minimized to low ppm levels (4–75 ppm) for most samples examined and also led to the improved thermal stability of the final materials. This represents the most efficient single method for removal of ruthenium residues from metathesis polymerization products.