The first example of a ferrocene-chelating heteroscorpionate, [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] ((fc(P,B))Li(THF)2, fc = 1,1'-ferrocenediyl) is described. Starting from a previously reported compound, fcBr(PPh2), a series of ferrocene derivatives, fc(PPh2)(B[OMe]2), [Li(OEt2)][fc(PPh2)(BH3)], [Li(THF)2][fc(PPh2)(BH[(3,5-Me)2pz]2)] (pz = pyrazole), was isolated and characterized. Compound (fc(P,B))Li(THF)2 allowed the synthesis of the corresponding nickel and zinc complexes, (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe. All compounds were characterized by NMR spectroscopy, while the zinc and nickel complexes were also characterized by X-ray crystallography. The redox behavior of (fc(P,B))NiCl, (fc(P,B))NiMe, (fc(P,B))ZnCl, and (fc(P,B))ZnMe was studied by cyclic voltammetry and supported by density functional theory calculations.

The synthesis of several novel nickel(II) and palladium(II) ferrocene-bis(phosphinimine) alkyl complexes containing iron-nickel and iron-palladium interactions is reported. The redox behavior of all complexes was evaluated electrochemically and chemically; in addition, reactions with weak nucleophiles, such as acetonitrile and olefins, were also investigated. DFT calculations were performed to understand the electronic structure of the alkyl metal complexes.

The ferrocene-chelating heteroscorpionate complex [(fc(PPh2){BH{(3,5-Me)2pz}2})PdMe] {(fcP,B)PdMe, fc = 1,1′-ferrocenediyl, pz = pyrazole} catalyzes the addition polymerization of norbornene and norbornene derivatives upon oxidation with [AcFc][BArF] {acetyl ferrocenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate}. In situ reduction of [(fcP,B)PdMe][BArF] in the presence of a substituted norbornene results in significant decrease of catalytic activity. Addition of one equivalent of oxidant restores the activity.

Poly(l-lactide) (PLA) is a bioderived and biodegradable polymer that has limited applications due to its hard and brittle nature. Incorporation of 1,3-trimethylene carbonate into PLA, in a block copolymer fashion, improves the mechanical properties, while retaining the biodegradability of the polymer, and broadens its range of applications. However, the preparation of 1,3-trimethylene carbonate (TMC)/l-lactide (LA) copolymers beyond diblock and triblock structures has not been reported, with explanations focusing mostly on thermodynamic reasons that impede the copolymerization of TMC after lactide. We discuss the preparation of multiblock copolymers via the ring opening polymerization (ROP) of LA and TMC, in a step-wise addition, by a ferrocene-chelating heteroscorpionate zinc complex, {[fc(PPh₂)(BH[(3,5-Me)₂pz]₂)]Zn(μ-OCH₂Ph)}₂ ([(fc^P,B)Zn(μ-OCH₂Ph)]₂, fc = 1,1'-ferrocenediyl, pz = pyrazole). The synthesis of up to pentablock copolymers, from various combinations of LA and TMC, was accomplished and the physical, thermal, and mechanical properties of the resulting copolymers evaluated.

Neutral zinc alkoxide complexes show high activity toward the ring-opening polymerization of cyclic esters and carbonates, to generate biodegradable plastics applicable in several areas. Herein, we use a ferrocene-chelating heteroscorpionate complex in redox-switchable polymerization reactions, and we show that it is a moderately active catalyst for the ring-opening polymerization of L-lactide, ɛ-caprolactone, trimethylene carbonate, and δ-valerolactone. Uniquely for this type of catalyst, the oxidized complex has a similar polymerization activity as the corresponding reduced compound, but displays significantly different rates of reaction in the case of trimethylene carbonate and δ-valerolactone. Investigations of the oxidized compound suggest the presence of an organic radical rather than an Fe(III) complex. Electronic structure and density functional theory (DFT) calculations were performed to support the proposed electronic states of the catalytic complex and to help explain the observed reactivity differences. The catalyst was also compared with a monomeric phenoxide complex to show the influence of the phosphine-zinc interaction on catalytic properties.

Footwear, carpet, automotive interiors, and multilayer packaging are examples of products manufactured from several types of polymers whose inextricability poses substantial challenges for recycling at the end of life. Here, we show that chemical circularity in mixed-polymer recycling becomes possible by controlling the rates of depolymerization of polydiketoenamines (PDK) over several orders of magnitude through molecular engineering. Stepwise deconstruction of mixed-PDK composites, laminates, and assemblies is chemospecific, allowing a prescribed subset of monomers, fillers, and additives to be recovered under pristine condition at each stage of the recycling process. We provide a theoretical framework to understand PDK depolymerization via acid-catalyzed hydrolysis and experimentally validate trends predicted for the rate-limiting step. The control achieved by PDK resins in managing chemical and material entropy points to wide-ranging opportunities for pairing circular design with sustainable manufacturing.