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Polyurethanes (PUs) are the sixth most commonly utilized plastic class, yet ∼80% of commodity material is landfilled or incinerated at the end of life. Disposal of thermosets is particularly problematic as cross-linking prevents the repurposing of disposed material. Thus, there is considerable interest in the development of PUs derived from inexpensive feedstocks that can be inherently chemically deconstructed. Ring opening metathesis polymerization (ROMP) of the naturally occurring sesquiterpene β-caryophyllene in the presence of dihydroxy chain terminators afforded the polyol hydroxy-terminated polycaryophyllene (HTPCR). Incorporation of HTPCR into PUs through reaction with polyisocyanates produced polymers with thermal and rheological properties comparable tomore » commodity materials. The feasibility of chemical degradation of both thermoplastic and thermoset materials was also demonstrated through ruthenium-mediated metathesis, utilizing the metathesis-active olefins within the repeat caryophyllene monomer unit. Overall, this work highlights the value of biorenewable, chemically reprocessable polysesquiterpenes in the PU space.« less

The application of bimolecular reductive elimination to the activation of iron catalysts for alkene–diene cycloaddition is described. Key to this approach was the synthesis, characterization, electronic structure determination, and ultimately solution stability of a family of pyridine(diimine) iron methyl complexes with diverse steric properties and electronic ground states. Both the aryl-substituted, (^MePDI)FeCH₃ and (^EtPDI)FeCH₃ (^RPDI = 2,6-(2,6-R₂-C₆H₃N=CMe)₂C₅H₃N), and the alkyl-substituted examples, (^CyAPDI)FeCH₃ (^CyAPDI = 2,6-(C₆H₁₁N=CMe)₂C₅H₃N), have molecular structures significantly distorted from planarity and S = 3/2 ground states. The related N-arylated derivative bearing 2,6-di-isopropyl aryl substituents, (^iPrPDI)FeCH₃, has an idealized planar geometry and exhibits spin crossover behavior from S =more » 1/2 to S = 3/2 states. At 23 °C under an N₂ atmosphere, both (^MePDI)FeCH₃ and (^EtPDI)FeCH₃ underwent reductive elimination of ethane to form the iron dinitrogen precatalysts, [(^MePDI)Fe(N₂)]₂(μ-N₂) and [(^EtPDI)Fe(N₂)]₂(μ-N₂), respectively, while (^iPrPDI)FeCH₃ proved inert to C–C bond formation. By contrast, addition of butadiene to all three iron methyl complexes induced ethane formation and generated the corresponding iron butadiene complexes, (^RPDI)Fe(η⁴-C₄H₆) (R = Me, Et, ⁱPr), known precatalysts for the [2+2] cycloaddition of olefins and dienes. Kinetic, crossover experiments, and structural studies were combined with magnetic measurements and Mössbauer spectroscopy to elucidate the electronic and steric features of the iron complexes that enable this unusual reductive elimination and precatalyst activation pathway. Furthermore, transmetalation of methyl groups between iron centers was fast at ambient temperature and independent of steric environment or spin state, while the intermediate dimer underwent the sterically controlled rate-determining reaction with either N₂ or butadiene to access a catalytically active iron compound.« less