More Like this

1. Structure and Mechanical Property of Highly Branched Polyethylene Thermoplastic Elastomers

   Peng, Bohao; Miyoshi, Toshikazu; Turney, Keaton; Eagan, James (March 2024, American Physical Society)

   Highly branched polyethylene (PE) thermoplastic elastomer (TPE)s can be synthesized using Brookhart-type α-diimine nickel and palladium catalysts, which show a range of branching number and identity. In this work, we aim at elucidating the structure-property relationship of various PE-TPEs through solution-state and solid-state 13C NMR spectroscopy and mechanical tensile testing. By applying solid-state NMR spectroscopy, DSC, and XRD, it was revealed that small degrees of crystallinity (< 5%) yields polyethylenes that are sufficiently reinforced to exhibit TPE behavior. Across PE samples with similar branching numbers, we relate the effects of branch identity, crystallinity, and molecular weight on the tunable mechanical properties. The structure-property relationship of the PE-TPEs will be discussed. 

   more » « less
2. Homolytic Pd ^II –C Bond Cleavage in the MILRad Process: Reversibility and Termination Mechanism

   https://doi.org/10.1021/acs.organomet.3c00277  

   Poli, Rinaldo; Nguyen, Dung; Liu, Yu-Sheng; Harth, Eva (August 2023, Organometallics)

   This work probed the thermal “switchability” from ethylene coordination/insertion to controlled radical polymerization of methyl acrylate (MA) for Brookhart-type α-diimine PdII catalysts. The investigation focused on the extremely bulky 2,6-bis(3,5-dimethylphenyl)-4-methylphenyl (Xyl4Ph) α-diimine N-substituents to probe reversible PdII–C bond activation in the MA-quenched Pd-capped PE intermediate and reversible trapping during radical MA polymerization. The substituent steric effect on the relative stability of various [PE–MA–PdII(ArN═CMeCMe═NAr)]+ chain-end structures and on the bond dissociation-free energy (BDFE) for the homolytic PdII–C bond cleavage has been assessed by DFT calculations at the full quantum mechanics (QM) and QM/molecular mechanics (QM/MM) methods. The structures comprise ester-chelated forms with the Pd atom bonded to the α, β, and γ C atoms as a result of 2,1 MA insertion into the PE–Pd bond and of subsequent chain walking, as well as related monodentate (ring-opened) forms resulting from the addition of MA or acetonitrile. The opened Cα-bonded form is electronically favored for smaller N-substituents, including 2,6-diisopropylphenyl (Dipp), particularly when MeCN is added, but the open Cγ-bonded form is preferred for the extremely bulky system with Ar = Xyl4Ph. The Pdα–C bond is the weakest one to cleave, with the BDFE decreasing as the Ar steric bulk is increased (31.8, 25.8, and 12.6 kcal mol–1 for Ph, Dipp, and Xyl4Ph, respectively). However, experimental investigations on the [PE–MA–PdII(ArN═CMeCMe═NAr)]+ (Ar = Xyl4Ph) macroinitiator do not show any evidence of radical formation under thermal activation conditions, while photolytic activation produces both TEMPO-trapped (TEMPO = 2,2,6,6-tetramethylpiperidinyloxy) and unsaturated MA-containing PE chains. The DFT investigation has highlighted a low-energy pathway for termination of the PE–MA• radicals by disproportionation, promoted by β-H elimination/dissociation and H-atom abstraction from the PdII–H intermediate by a second radical. This phenomenon appears to be the main reason for the failure of this PdII system to control the radical polymerization of MA by the OMRP (OMRP = organometallic-mediated radical polymerization) mechanism. 

   more » « less
3. Proton-Coupled, Low-Energy Pathway for Electrocatalytic CO ₂ Reduction at Re(Diimine) Complexes with a Conjugated Pyrazinyl Moiety

   https://doi.org/10.1021/acs.inorgchem.2c02400  

   Chandy, Sruthy K.; Bowers, Scott A.; Yin, Minyang; Liu, Lu; Raghavachari, Krishnan; Li, Liang-shi (October 2022, Inorganic Chemistry)

   Large conjugated carbon framework has been incorporated as the diimine ligand for Re(α-diimine)(CO)3Cl complexes with a pyrazinyl linkage, either to increase energy efficiency or to turn them into heterogeneous catalysts for selective electrocatalytic CO2 reduction. However, there exists a nonmonotonic dependence of CO2 reduction overpotential on the conjugation size of the ligands. Understanding its origin could facilitate heterogenization of molecular catalysts with improved energy efficiency. Here, we show that the conjugated pyrazinyl moiety plays a crucial role in catalysis by enabling a proton-coupled, lower-energy pathway for CO2 reduction. With ligands of moderate size, the pathway leads to previously unknown intermediates and decreases CO2 reduction overpotential. Because the pathway hinges on the basicity of the pyrazinyl nitrogen, we propose that it imposes a limit on the conjugation size of the ligand for the pathway to be effective. 

   more » « less
4. Chain-Straightening Polymerization of Olefins to Form Polar Functionalized Semicrystalline Polyethylene

   https://doi.org/10.1021/acs.organomet.2c00366  

   Eagan, James M.; Padilla-Vélez, Omar; O’Connor, Kyle S.; MacMillan, Samantha N.; LaPointe, Anne M.; Coates, Geoffrey W. (September 2022, Organometallics)

   We report the design and synthesis of an α-diimine PdII catalyst that copolymerizes functionalized and long chain α-olefins to produce semicrystalline polyethylene materials. Through a chain-straightening polymerization mechanism, the catalyst afforded high-melting point polymers with Tm values of up to 120 °C. The chain-straightening polymerization operates with high [ω,1]-insertion selectivity at high alkene concentrations and with varying α-olefin chain lengths, including propylene. The Pd catalyst can copolymerize 1-decene and methyl decenoate into semicrystalline ester-functionalized polymers with incorporation percentages proportional to the comonomer ratio (up to 13 mol %). 13C nuclear magnetic resonance and isotope labeling studies revealed that the improved selectivity relative to those of other systems arises from a high selectivity for [2,1]-insertion (96%) coupled with rapid chain-walking for a total of 90 mol % of 1-decene undergoing net [10,1]-insertion. 

   more » « less
5. Sensitized and Self‐Sensitized Photocatalytic Carbon Dioxide Reduction Under Visible Light with Ruthenium Catalysts Shows Enhancements with More Conjugated Pincer Ligands

   https://doi.org/10.1002/ejic.202101016  

   Das, Sanjit; Nugegoda, Dinesh; Yao, Wenzhi; Qu, Fengrui; Figgins, Matthew_T; Lamb, Robert_W; Webster, Charles_Edwin; Delcamp, Jared_H; Papish, Elizabeth_T (February 2022, European Journal of Inorganic Chemistry)

   Abstract A new method to synthesize complexes of the type [(CNC)Ru^II(NN)L]ⁿ⁺has been introduced, where CNC is a tridentate pincer composed of two (benz)imidazole derived NHC rings and a pyridyl ring, NN is a bidentate aromatic diimine ligand, L=bromide or acetonitrile, and n=1 or 2. Following this new method a series of six new complexes has been synthesized and characterized by spectroscopic, analytic, crystallographic, and computational methods. Their electrochemical properties have been studiedviacyclic voltammetry under both N₂and CO₂atmospheres. Photocatalytic reduction of CO₂to CO was performed using these complexes both in the presence (sensitized) and absence (self‐sensitized) of an external photosensitizer. This study evaluates the effect of different CNC, NN, and L ligands in sensitized and self‐sensitized photocatalysis. Catalysts bearing the benzimidazole derived CNC pincer show much better activity for both sensitized and self‐sensitized photocatalysis as compared to catalysts bearing the imidazole derived CNC pincer. Furthermore, self‐sensitized photocatalysis requires a diimine ligand for CO₂reduction with catalyst2_ACNbeing the most active catalyst in this series with TON=85 and TOF=22 h⁻¹with an electron donating 4,4′‐dimethyl‐2,2′‐bipyridyl (dmb) ligand and a benzimidazole derived CNC pincer. 

   more » « less