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1. Cu( i )–O ₂ oxidation reactions in a fluorinated all-O-donor ligand environment

   https://doi.org/10.1039/C8DT05028G  

   Brazeau, Sarah E.; Doerrer, Linda H. (April 2019, Dalton Transactions)

   Investigation of Cu–O 2 oxidation reactivity is important in biological and anthropogenic chemistry. Zeolites are one of the most promising Cu/O based oxidation catalysts for development of industrial-scale CH 4 to CH 3 OH conversion. Their oxidation mechanisms are not well understood, however, highlighting the importance of the investigation of molecular Cu( i )–O 2 reactivity with O-donor complexes. Herein, we give an overview of the synthesis, structural properties, and O 2 reactivity of three different series of O-donor fluorinated Cu( i ) alkoxides: K[Cu(OR) 2 ], [(Ph 3 P)Cu(μ-OR) 2 Cu(PPh 3 )], and K[(R 3 P)Cu(pin F )], in which OR = fluorinated monodentate alkoxide ligands and pin F = perfluoropinacolate. This breadth allowed for the exploration of the influence of the denticity of the ligand, coordination number, the presence of phosphine, and K⋯F/O interactions on their O 2 reactivity. K⋯F/O interactions were required to activate O 2 in the monodentate-ligand-only family, whereas these connections did not affect O 2 activation in the bidentate complexes, potentially due to the presence of phosphine. Both families formed trisanionic, trinuclear cores of the form {Cu 3 (μ 3 -O) 2 } 3− . Intramolecular and intermolecular substrate oxidation were also explored and found to be influenced by the fluorinated ligand. Namely, {Cu 3 (μ 3 -O) 2 } 3− from K[Cu(OR) 2 ] could perform both monooxygenase reactivity and oxidase catalysis, whereas those from K[(R 3 P)Cu(pin F )] could only perform oxidase catalysis. 

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2. Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

   https://doi.org/10.1002/anie.202105421  

   Vargo, Natasha P.; Harland, Jill B.; Musselman, Bradley W.; Lehnert, Nicolai; Ertem, Mehmed Z.; Robinson, Jerome R. (July 2021, Angewandte Chemie International Edition)

   Abstract Coupled dinuclear copper oxygen cores (Cu₂O₂) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O₂transport and substrate oxidation in many organisms.μ‐1,2‐cisperoxido dicopper cores (^CP) have been proposed as key structures in the early stages of O₂binding in these proteins; their reversible isomerization to other Cu₂O₂cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic^CPcores in biological and synthetic systems, the properties and reactivity of^CPCu₂O₂species remain largely unexplored. Herein, we report the reversible interconversion ofμ‐1,2‐transperoxido (^TP) and^CPdicopper cores. Ca^IImediates this process by reversible binding at the Cu₂O₂core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O₂activation in biomimetic systems. 

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3. Enabling coherent BaZrO ₃ nanorods/YBa ₂ Cu ₃ O _7−x interface through dynamic lattice enlargement in vertical epitaxy of BaZrO ₃ /YBa ₂ Cu ₃ O _7−x nanocomposites

   https://doi.org/10.1088/1361-6668/ac4aff  

   Wu, Judy Z; Ogunjimi, Victor; Sebastian, Mary Ann; Zhang, Di; Jian, Jie; Huang, Jijie; Zhang, Yifan; Gautam, Bibek; Haugan, Timothy; Wang, Haiyan (February 2022, Superconductor Science and Technology)

   Abstract One-dimensional c -axis-aligned BaZrO 3 (BZO) nanorods are regarded as strong one-dimensional artificial pinning centers (1D-APCs) in BZO-doped YaBa 2 Cu 3 O 7− x (BZO/YBCO) nanocomposite films. However, a microstructure analysis has revealed a defective, oxygen-deficient YBCO column around the BZO 1D-APCs due to the large lattice mismatch of ∼7.7% between the BZO (3a = 1.26 nm) and YBCO (c = 1.17 nm), which has been blamed for the reduced pinning efficiency of BZO 1D-APCs. Herein, we report a dynamic lattice enlargement approach on the tensile strained YBCO lattice during the BZO 1D-APCs growth to induce c -axis elongation of the YBCO lattice up to 1.26 nm near the BZO 1D-APC/YBCO interface via Ca/Cu substitution on single Cu-O planes of YBCO, which prevents the interfacial defect formation by reducing the BZO/YBCO lattice mismatch to ∼1.4%. Specifically, this is achieved by inserting thin Ca 0.3 Y 0.7 Ba 2 Cu 3 O 7− x (CaY-123) spacers as the Ca reservoir in 2–6 vol.% BZO/YBCO nanocomposite multilayer (ML) films. A defect-free, coherent BZO 1D-APC/YBCO interface is confirmed in transmission electron microscopy and elemental distribution analyses. Excitingly, up to five-fold enhancement of J c ( B ) at magnetic field B = 9.0 T// c -axis and 65 K–77 K was obtained in the ML samples as compared to their BZO/YBCO single-layer (SL) counterpart’s. This has led to a record high pinning force density F p together with significantly enhanced B max at which F p reaches its maximum value F p,max for BZO 1D-APCs at B // c -axis. At 65 K, the F p,max ∼158 GN m −3 and B max ∼ 8.0 T for the 6% BZO/YBCO ML samples represent a significant enhancement over F p,max ∼ 36.1 GN m −3 and B max ∼ 5.0 T for the 6% BZO/YBCO SL counterparts. This result not only illustrates the critical importance of a coherent BZO 1D-APC/YBCO interface in the pinning efficiency, but also provides a facile scheme to achieve such an interface to restore the pristine pinning efficiency of the BZO 1D-APCs. 

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4. HAA by the first {Mn( iii )OH} complex with all O-donor ligands

   https://doi.org/10.1039/d3sc01971c  

   Moore, Shawn M.; Sun, Chen; Steele, Jennifer L.; Laaker, Ellen M.; Rheingold, Arnold L.; Doerrer, Linda H. (July 2023, Chemical Science)

   There is considerable interest in MnOH x moieties, particularly in the stepwise changes in those O–H bonds in tandem with Mn oxidation state changes. The reactivity of aquo-derived ligands, {MOH x }, is also heavily influenced by the electronic character of the other ligands. Despite the prevalence of oxygen coordination in biological systems, preparation of mononuclear Mn complexes of this type with all O-donors is rare. Herein, we report several Mn complexes with perfluoropinacolate (pin F ) 2− including the first example of a crystallographically characterized mononuclear {Mn( iii )OH} with all O-donors, K 2 [Mn(OH)(pin F ) 2 ], 3. Complex 3 is prepared via deprotonation of K[Mn(OH 2 )(pin F ) 2 ], 1, the p K a of which is estimated to be 18.3 ± 0.3. Cyclic voltammetry reveals quasi-reversible redox behavior for both 1 and 3 with an unusually large Δ E p , assigned to the Mn( iii / ii ) couple. Using the Bordwell method, the bond dissociation free energy (BDFE) of the O–H bond in {Mn( ii )–OH 2 } is estimated to be 67–70 kcal mol −1 . Complex 3 abstracts H-atoms from 1,2-diphenylhydrazine, 2,4,6-TTBP, and TEMPOH, the latter of which supports a PCET mechanism. Under basic conditions in air, the synthesis of 1 results in K 2 [Mn(OAc)(pin F ) 2 ], 2, proposed to result from the oxidation of Et 2 O to EtOAc by a reactive Mn species, followed by ester hydrolysis. Complex 3 alone does not react with Et 2 O, but addition of O 2 at low temperature effects the formation of a new chromophore proposed to be a Mn( iv ) species. The related complexes K(18C6)[Mn( iii )(pin F ) 2 ], 4, and (Me 4 N) 2 [Mn( ii )(pin F ) 2 ], 5, have also been prepared and their properties discussed in relation to complexes 1–3. 

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5. Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl ₂ (OR) ₂ complexes

   https://doi.org/10.1039/d0dt03917a  

   Grass, Amanda; Kulathungage, Lakshani Wathsala; Wannipurage, Duleeka; Yousif, Maryam; Ward, Cassandra L.; Groysman, Stanislav (February 2021, Dalton Transactions)

   null (Ed.)

   Reaction of LiOC t Bu 2 Ph with TlPF 6 forms the dimeric Tl 2 (OC t Bu 2 Ph) 2 complex, a rare example of a homoleptic thallium alkoxide complex demonstrating formally two-coordinate metal centers. Characterization of Tl 2 (OC t Bu 2 Ph) 2 by 1 H and 13 C NMR spectroscopy and X-ray crystallography reveals the presence of two isomers differing by the mutual conformation of the alkoxide ligands, and by the planarity of the central Tl–O–Tl–O plane. Tl 2 (OC t Bu 2 Ph) 2 serves as a convenient precursor to the formation of old and new [M(OC t Bu 2 Ph) n ] complexes (M = Cr, Fe, Cu, Zn), including a rare example of T-shaped Zn(OC t Bu 2 Ph) 2 (THF) complex, which could not be previously synthesized using more conventional LiOR/HOR precursors. The reaction of [Ru(cymene)Cl 2 ] 2 with Tl 2 (OC t Bu 2 Ph) 2 results in the formation of a ruthenium( ii ) alkoxide complex. For ruthenium, the initial coordination of the alkoxide triggers C–H activation at the ortho -H of [OC t Bu 2 Ph] which results in its bidentate coordination. In addition to Tl 2 (OC t Bu 2 Ph) 2 , related Tl 2 (OC t Bu 2 (3,5-Me 2 C 6 H 3 )) 2 was also synthesized, characterized, and shown to exhibit similar reactivity with iron and ruthenium precursors. Synthetic, structural, and spectroscopic characterizations are presented. 

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