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1. Reaction Mechanism Underlying Pd(II)-Catalyzed Oxidative Coupling of Ethylene and Benzene to Form Styrene: Identification of a Cyclic Mono-Pd ^II Bis-Cu ^II Complex as the Active Catalyst

   https://doi.org/10.1021/acs.organomet.2c00183  

   Musgrave, Charles B.; Bennett, Marc T.; Ellena, Jeffrey F.; Dickie, Diane A.; Gunnoe, T. Brent; Goddard, William A. (July 2022, Organometallics)

   A recent advance in the synthesis of alkenylated arenes was the demonstration that the Pd(OAc)2 catalyst precursor gives >95% selectivity toward styrene from ethylene and benzene under optimized conditions using excess Cu(II) carboxylate as the in situ oxidant [ Organometallics 2019, 38(19), 3532−3541]. To understand the mechanism underlying this catalysis, we applied density functional theory (DFT) calculations in combination with experimental studies. From DFT calculations, we determined the lowest-energy multimetallic Pd and Pd–Cu mixed metal species as possible catalyst precursors. From the various structures, we determined the cyclic heterotrinuclear complex PdCu2(μ-OAc)6 to be the global minimum in Gibbs free energy under conditions of excess Cu(II). For cyclic PdCu2(μ-OAc)6 and the parent [Pd(μ-OAc)2]3, we evaluated the barriers for benzene C–H activation through concerted metalation deprotonation (CMD). The PdCu2(μ-OAc)6 cyclic trimer leads to a CMD barrier of 33.5 kcal/mol, while the [Pd(μ-OAc)2]3 species leads to a larger CMD barrier at >35 kcal/mol. This decrease in the CMD barrier arises from the insertion of Cu(II) into the trimetallic species. Because cyclic PdCu2(μ-OAc)6 is likely the predominant species under experimental conditions (the Cu to Pd ratio is 480:1 at the start of catalysis) with a predicted CMD barrier within the range of the experimentally determined activation barrier, we propose that cyclic PdCu2(μ-OAc)6 is the Pd species responsible for catalysis and report a full reaction mechanism based on DFT calculations. For catalytic conversion of benzene and ethylene to styrene at 120 °C using Pd(OAc)2 as the catalyst precursor and Cu(OPiv)2 (OPiv = pivalate) as the oxidant, an induction period of ∼1 h was observed, followed by catalysis with a turnover frequency of ∼2.3 × 10–3 s–1. In situ1H NMR spectroscopy experiments indicate that during the induction period, Pd(OAc)2 is likely converted to cyclic PdCu2(η2-C2H4)3(μ-OPiv)6, which is consistent with the calculations and consistent with the proposal that the active catalyst is the ethylene-coordinated heterotrinuclear complex cyclic PdCu2(η2-C2H4)3(μ-OPiv)6. 

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2. Consequences of exchange-site heterogeneity and dynamics on the UV-visible spectrum of Cu-exchanged SSZ-13

   https://doi.org/10.1039/c8sc05056b  

   Li, Hui; Paolucci, Christopher; Khurana, Ishant; Wilcox, Laura N.; Göltl, Florian; Albarracin-Caballero, Jonatan D.; Shih, Arthur J.; Ribeiro, Fabio H.; Gounder, Rajamani; Schneider, William F. (February 2019, Chemical Science)

   The speciation and structure of Cu ions and complexes in chabazite (SSZ-13) zeolites, which are relevant catalysts for nitrogen oxide reduction and partial methane oxidation, depend on material composition and reaction environment. Ultraviolet-visible (UV-Vis) spectra of Cu-SSZ-13 zeolites synthesized to contain specific Cu site motifs, together with ab initio molecular dynamics and time-dependent density functional theory calculations, were used to test the ability to relate specific spectroscopic signatures to specific site motifs. Geometrically distinct arrangements of two framework Al atoms in six-membered rings are found to exchange Cu 2+ ions that become spectroscopically indistinguishable after accounting for the finite-temperature fluctuations of the Cu coordination environment. Nominally homogeneous single Al exchange sites are found to exchange a heterogeneous mixture of [CuOH] + monomers, O- and OH-bridged Cu dimers, and larger polynuclear complexes. The UV-Vis spectra of the latter are sensitive to framework Al proximity, to precise ligand environment, and to finite-temperature structural fluctuations, precluding the precise assignment of spectroscopic features to specific Cu structures. In all Cu-SSZ-13 samples, these dimers and larger complexes are reduced by CO to Cu + sites at 523 K, leaving behind isolated [CuOH] + sites with a characteristic spectroscopic identity. The various mononuclear and polynuclear Cu 2+ species are distinguishable by their different responses to reducing environments, with implications for their relevance to catalytic redox reactions. 

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3. Kinetics and Modeling of Counter-Current Leaching of Waste Random-Access Memory Chips in a Cu-NH3-SO4 System Utilizing Cu(II) as an Oxidizer

   https://doi.org/10.3390/ma16186274  

   Lin, Peijia; Werner, Joshua; Ali, Zulqarnain Ahmad; Bertucci, Lucas; Groppo, Jack (September 2023, Materials)

   The leaching of Cu in ammoniacal solutions has proven an efficient method to recover Cu from waste printed circuit boards (WPCBs) that has used by many researchers over the last two decades. This study investigates the feasibility of a counter-current leaching circuit that would be coupled with an electrowinning (EW) cell. To accomplish this objective, the paper is divided into three parts. In Part 1, a leaching kinetic framework is developed from a set of experiments that were designed and conducted using end-of-life waste RAM chips as feed sources and Cu(II)-ammoniacal solution as the lixiviant. Various processing parameters, such as particle size, stirring rates, initial Cu(II) concentrations, and temperatures, were evaluated for their effects on the Cu recovery and the leaching rate. It was found that the particle size and initial Cu(II) concentration were the two most important factors in Cu leaching. Using a 1.2 mm particle size diameter and 40 g/L of initial Cu(II) concentration, a maximum Cu recovery of 96% was achieved. The Zhuravlev changing-concentration model was selected to develop the empirically fitted kinetic coefficients. In Part 2, kinetic data were adapted into a leaching function suitable for continuously stirred tank reactors. This was achieved via using the coefficients from the Zhuravlev model and adapting them to the Jander constant concentration model for use in the counter-current circuit model. Part 3 details the development of a counter-current circuit model based on the relevant kinetic model, and the circuit performance was modeled to provide a tool that would allow the exploration of maximum copper recovery whilst minimizing the Cu(II) reporting to electrowinning. A 4-stage counter-current circuit was modeled incorporating a feed of 35 g/L of Cu(II), achieving a 4.12 g/L Cu(II) output with 93% copper recovery. 

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4. Encapsulation of tricopper cluster in a synthetic cryptand enables facile redox processes from Cu ^I Cu ^I Cu ^I to Cu ^II Cu ^II Cu ^II states

   https://doi.org/10.1039/D0SC05441K  

   Zhang, Weiyao; Moore, Curtis E.; Zhang, Shiyu (March 2021, Chemical Science)

   null (Ed.)

   One-pot reaction of tris(2-aminoethyl)amine (TREN), [Cu I (MeCN) 4 ]PF 6 , and paraformaldehyde affords a mixed-valent [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 complex. The macrocyclic azacryptand TREN4 contains four TREN motifs, three of which provide a bowl-shape binding pocket for the [Cu 3 (μ 3 -OH)] 3+ core. The fourth TREN caps on top of the tricopper cluster to form a cryptand, imposing conformational constraints and preventing solvent interaction. Contrasting the limited redox capability of synthetic tricopper complexes reported so far, [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 exhibits several reversible single-electron redox events. The distinct electrochemical behaviors of [ TREN4 Cu II Cu I Cu I (μ 3 -OH)](PF 6 ) 3 and its solvent-exposed analog [ TREN3 Cu II Cu II Cu II (μ 3 -O)](PF 6 ) 4 suggest that isolation of tricopper core in a cryptand enables facile electron transfer, allowing potential application of synthetic tricopper complexes as redox catalysts. Indeed, the fully reduced [ TREN4 Cu I Cu I Cu I (μ 3 -OH)](PF 6 ) 2 can reduce O 2 under acidic conditions. The geometric constraints provided by the cryptand are reminiscent of Nature's multicopper oxidases (MCOs). For the first time, a synthetic tricopper cluster was isolated and fully characterized at Cu I Cu I Cu I ( 4a ), Cu II Cu I Cu I ( 4b ), and Cu II Cu II Cu I ( 4c ) states, providing structural and spectroscopic models for many intermediates in MCOs. Fast electron transfer rates (10 5 to 10 6 M −1 s −1 ) were observed for both Cu I Cu I Cu I /Cu II Cu I Cu I and Cu II Cu I Cu I /Cu II Cu II Cu I redox couples, approaching the rapid electron transfer rates of copper sites in MCO. 

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5. The Search for Molecular Corks Beyond Carbon Monoxide: A Quantum Mechanical Study of N-Heterocyclic Carbene Adsorption on Pd/Cu(111) and Pt/Cu(111)

   Simpson, Scott (March 2022, ACS Spring 2022)

   Periodic Density Functional Theory calculations reveal the potential application of 10 imidazole based N-heterocyclic carbenes (NHCs) to behave as “molecular corks” for hydrogen storage on single atom alloys, comprised of Pd/Cu(111) or Pt/Cu(111). Calculations show that functionalizing the NHC with different electron withdrawing/donating functional groups results in different binding energies of the NHC with the alloy surfaces. The results are compared to DFT calculations of carbon monoxide bound to these alloys. The Huynh electronic parameter (HEP) is calculated for several simple imidazole NHCs to gauge σ-donor ability, while Se-NMR and P-NMR calculations of selenourea derivatives and carbene-phosphinidene adducts, respectively, have been utilized to gauge π-acidity of the NHCs. It is demonstrated that consideration of both σ and π donating/accepting ability must be considered when predicting the surface-adsorbate binding energy. It was found that electron withdrawing groups tend to weaken the NHC-surface interaction while electron donating substituents tend to strengthen the interaction. 

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