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Developing effective catalysis to address end-of-life Nylon pollution is urgent yet remains underdeveloped. Nylon-6 is a resilient synthetic plastic and a major contributor to ocean pollution. Here, we report a metallocene catalytic system based on earth-abundant early transition and lanthanide metals that mediates Nylon-6 depolymerization at unprecedented rates up to 810 (ε-caprolactam)$ mol(Cat.)1$h1 at 240C in R99% yield. This solventless process operates with catalyst loadings as low as 0.04 mol % at temperatures as low as 220C—themildest Nylon-6 depolymerization conditions reported to date. This metallocene catalysis can be carried out in a simulated continuous process, and the resulting ε-caprolactam can be re-polymerized to higher-quality Nylon-6. Experimental and DFT analyses identify effective depolymerization pathways involving catalytic intra-Nylon-chain ‘‘unzipping’’ assisted by p-ligand effects and inter-chain ‘‘hopping.’’ A robust chelating ansa-yttrocene is particularly effective in depolymerizing diverse commodity end-of-life articles, such as fishing nets, carpets, clothing, and plastic mixtures. 

Carbonyl bond hydroboration is a valuable synthetic route to functionalized alcohols but relies on sometimes unselective and sluggish reagents. While rapid and selective aldehyde and ketone hydroboration mediated by trisamidolanthanide catalysts is known, the origin of the selectivity is not well-understood and is the subject of this contribution. Here the aldehyde and ketone HBpin hydroboration reaction mechanisms catalyzed by La[N(SiMe 3 ) 2 ] 3 are investigated both experimentally and theoretically. The results support initial carbonyl oxygen coordination to the acidic La center, followed by intramolecular ligand-assisted hydroboration of the carbonyl moiety by bound HBpin. Interestingly, ketone hydroboration has a higher energetic barrier than that of aldehydes due to the increased steric encumbrance and decreased electrophilicity. Utilizing NMR spectroscopy and X-ray diffraction, a bidentate acylamino lanthanide complex associated with the aldehyde hydroboration is isolated and characterized, consistent with the relative reaction rates. Furthermore, an aminomonoboronate–lanthanide complex produced when the La catalyst is exposed to excess HBpin is isolated and characterized by X-ray diffraction, illuminating unusual aminomonoboronate coordination. These results shed new light on the origin of the catalytic activity patterns, reveal a unique ligand-assisted hydroboration pathway, and uncover previously unknown catalyst deactivation pathways. 

Polyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to their inert saturated hydrocarbon connectivities. Here a very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on a highly Brønsted acidic sulfated alumina support and characterized by a broad array of experimental and theoretical techniques, is shown to mediate the rapid hydrogenolytic cleavage of molecular and macromolecular saturated hydrocarbons under mild conditions, with catalytic onset as low as 90 °C/0.5 atm H₂with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH₂units)·mol(Zr)⁻¹·h⁻¹at 200 °C/2 atm H₂pressure. Under similar solventless conditions, polyethylene-co−1-octene, isotactic polypropylene, and a post-consumer food container cap are rapidly hydrogenolyzed to low molecular mass hydrocarbons. Regarding mechanism, theory and experiment identify a turnover-limiting C-C scission pathway involvingß-alkyl transfer rather than the more common σ-bond metathesis.

 

The novel electrophilic organo‐tantalum catalyst AlS/TaNp_x(1) (Np=neopentyl) is prepared by chemisorption of the alkylidene Np₃Ta=CH^tBu onto highly Brønsted acidic sulfated alumina (AlS). The proposed catalyst structure is supported by EXAFS, XANES, ICP, DRIFTS, elemental analysis, and SSNMR measurements and is in good agreement with DFT analysis. Catalyst1is highly effective for the hydrogenolysis of diverse linear and branched hydrocarbons, ranging from C2 to polyolefins. To the best of our knowledge,1exhibits one of the highest polyolefin hydrogenolysis activities (9,800 (CH₂units) ⋅ mol(Ta)⁻¹ ⋅ h⁻¹at 200 °C/17 atm H₂) reported to date in the peer‐reviewed literature. Unlike the AlS/ZrNp₂analog, the Ta catalyst is more thermally stable and offers multiple potential C−C bond activation pathways. For hydrogenolysis, AlS/TaNp_xis effective for a wide variety of pre‐ and post‐consumer polyolefin plastics and is not significantly deactivated by standard polyolefin additives at typical industrial concentrations.

 

The novel electrophilic organo‐tantalum catalyst AlS/TaNp_x(1) (Np=neopentyl) is prepared by chemisorption of the alkylidene Np₃Ta=CH^tBu onto highly Brønsted acidic sulfated alumina (AlS). The proposed catalyst structure is supported by EXAFS, XANES, ICP, DRIFTS, elemental analysis, and SSNMR measurements and is in good agreement with DFT analysis. Catalyst1is highly effective for the hydrogenolysis of diverse linear and branched hydrocarbons, ranging from C2 to polyolefins. To the best of our knowledge,1exhibits one of the highest polyolefin hydrogenolysis activities (9,800 (CH₂units) ⋅ mol(Ta)⁻¹ ⋅ h⁻¹at 200 °C/17 atm H₂) reported to date in the peer‐reviewed literature. Unlike the AlS/ZrNp₂analog, the Ta catalyst is more thermally stable and offers multiple potential C−C bond activation pathways. For hydrogenolysis, AlS/TaNp_xis effective for a wide variety of pre‐ and post‐consumer polyolefin plastics and is not significantly deactivated by standard polyolefin additives at typical industrial concentrations.

 

Using a mechanism‐based solvent‐free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air‐ and moisture‐stable catalysts, Hf(OTf)₄and Pd/C, under 1 atm H₂, affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)₄catalyzes a mildly exergonic retro‐hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.

 

Using a mechanism‐based solvent‐free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air‐ and moisture‐stable catalysts, Hf(OTf)₄and Pd/C, under 1 atm H₂, affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf)₄catalyzes a mildly exergonic retro‐hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.