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1. Probing copper-boron interactions in the Cu ₂ B ₈ ⁻ bimetallic cluster

   https://doi.org/10.1116/6.0001833  

   Kulichenko, Maksim; Chen, Wei-Jia; Choi, Hyun Wook; Yuan, Dao-Fu; Boldyrev, Alexander I.; Wang, Lai-Sheng (July 2022, Journal of Vacuum Science & Technology A)

   Borophenes are atom-thin boron layers that can be grown on coinage metal substrates and have become an important class of synthetic 2D nanomaterials. The interactions between boron and substrates are critical to understand the growth mechanisms of borophenes. Here, we report an investigation of copper-boron interactions in the Cu 2 B 8 − bimetallic cluster using photoelectron spectroscopy and quantum chemical calculations. Well-resolved photoelectron spectra are obtained at several photon energies and are combined with theoretical calculations to elucidate the structures and bonding of Cu 2 B 8 − . Global minimum searches reveal that Cu 2 B 8 − consists of a Cu 2 dimer atop a B 8 molecular wheel with a long Cu–Cu bond length close to that in Cu 2 + . Chemical bonding analyses indicate that there is clear charge transfer from Cu 2 to B 8 , and the Cu 2 B 8 − cluster can be viewed as a [Cu 2 + ]-borozene complex, [Cu 2 + ][B 8 2– ]. In the neutral cluster, no Cu–Cu bond exists and Cu 2 B 8 consists of two Cu + centers interacting with doubly aromatic B 8 2− borozene. The charge transfer interactions between Cu and boron in the Cu 2 B 8 − cluster are analogous to charge transfer from the copper substrate to the first borophene layer recently reported to be critical in the growth of bilayer borophenes on a Cu(111) substrate. 

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2. Expanded Inverse-Sandwich Complexes of Lanthanum Borides: La ₂ B ₁₀ ^– and La ₂ B ₁₁ ^–

   https://doi.org/10.1021/acs.jpca.1c01149  

   Jiang, Zhi-Yu; Chen, Teng-Teng; Chen, Wei-Jia; Li, Wan-Lu; Li, Jun; Wang, Lai-Sheng (April 2021, The Journal of Physical Chemistry A)

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3. Investigation of Pb–B Bonding in PbB ₂ (BO) _n ⁻ ( n = 0–2): Transformation from Aromatic PbB ₂ ⁻ to Pb[B ₂ (BO) ₂ ] ^−/0 Complexes with BB Triple Bonds

   https://doi.org/10.1039/D3CP02800C  

   Chen, Qiang; Chen, Wei-Jia; Wu, Xin-Yao; Chen, Teng-Teng; Yuan, Rui-Nan; Lu, Hai-Gang; Yuan, Dao-Fu; Li, Si-Dian; Wang, Lai-Sheng (February 2024, Physical Chemistry Chemical Physics)

   Joint photoelectron spectroscopy and first-principles theory investigations indicate that the Pb-doped PbB₂(BO)_n⁻clusters (n= 0−2) undergo a transformation from σ + π doubly aromatic triangle PbB₂⁻to PbB₄(BO)₂^−/0complexes with a B≡B triple bond. 

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4. DFT Analysis of Methane C−H Activation and Over‐Oxidation by [Cu ₂ O] ²⁺ and [Cu ₂ O ₂ ] ²⁺ Sites in Zeolite Mordenite: Intra‐ versus Inter‐site Over‐Oxidation

   https://doi.org/10.1002/cphc.202100580  

   Panthi, Dipak; Adeyiga, Olajumoke; Odoh, Samuel_O (October 2021, ChemPhysChem)

   Abstract Methane over‐oxidation by copper‐exchanged zeolites prevents realization of high‐yield catalytic conversion. However, there has been little description of the mechanism for methane over‐oxidation at the copper active sites of these zeolites. Using density functional theory (DFT) computations, we reported that tricopper [Cu₃O₃]²⁺active sites can over‐oxidize methane. However, the role of [Cu₃O₃]²⁺sites in methane‐to‐methanol conversion remains under debate. Here, we examine methane over‐oxidation by dicopper [Cu₂O]²⁺and [Cu₂O₂]²⁺sites using DFT in zeolite mordenite (MOR). For [Cu₂O₂]²⁺, we considered the μ‐(η²:η²) peroxo‐, and bis(μ‐oxo) motifs. These sites were considered in the eight‐membered (8MR) ring of MOR. μ‐(η²:η²) peroxo sites are unstable relative to the bis(μ‐oxo) motif with a small interconversion barrier. Unlike [Cu₂O]²⁺which is active for methane C−H activation, [Cu₂O₂]²⁺has a very large methane C−H activation barrier in the 8MR. Stabilization of methanol and methyl at unreacted dicopper sites however leads to over‐oxidation via sequential hydrogen atom abstraction steps. For methanol, these are initiated by abstraction of the CH₃group, followed by OH and can proceed near 200 °C. Thus, for [Cu₂O]²⁺and [Cu₂O₂]²⁺species, over‐oxidation is an inter‐site process. We discuss the implications of these findings for methanol selectivity, especially in comparison to the intra‐site process for [Cu₃O₃]²⁺sites and the role of Brønsted acid sites. 

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5. Boron‐Made N ₂ : Realization of a B≡B Triple Bond in the B ₂ Al ₃ ⁻ Cluster

   https://doi.org/10.1002/chem.202001159  

   Fedik, Nikita; Mu, Chaonan; Popov, Ivan A.; Wang, Wei; Wang, Jie; Wang, Haopeng; Bowen, Kit H.; Boldyrev, Alexander I.; Zhang, Xinxing (June 2020, Chemistry – A European Journal)