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1. Formation of Nanoscale [Ge 4 O 16 Al 48 (OH) 108 (H 2 O) 24 ] 20+ from Condensation of ϵ‐GeAl 12 8+ Keggin Polycations**

   https://doi.org/10.1002/ange.202017321  

   Shohel, Mohammad ; Bjorklund, Jennifer L. ; Smith, Jack A. ; Kravchuk, Dmytro V. ; Mason, Sara E. ; Forbes, Tori Z. ( March 2021 , Angewandte Chemie)

   Keggin‐type polyaluminum cations belong to a unique class of compounds with their large positive charge, hydroxo bridges, and divergent isomerization/oligomerization. Previous reports indicated that oligomerization of this species can only occur through one isomer (δ), but herein we report the isolation of largest Keggin‐type cluster that occurs through self‐condensation of four ϵ‐isomers ϵ‐GeAl₁₂⁸⁺to form [Ge₄O₁₆Al₄₈(OH)₁₀₈(H₂O)₂₄]²⁰⁺cluster (Ge₄Al₄₈). The cluster was crystallized and structurally characterized by single‐crystal X‐ray diffraction (SCXRD) and the elemental composition was confirmed by ICP‐MS and SEM‐EDS. Additional dynamic light scattering experiments confirms the presence of theGe₄Al₄₈in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of ϵ‐isomer is the key for the formation ofGe₄Al₄₈because it activates deprotonation at key surface sites that control the self‐condensation process.

    

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2. Formation of Nanoscale [Ge 4 O 16 Al 48 (OH) 108 (H 2 O) 24 ] 20+ from Condensation of ϵ‐GeAl 12 8+ Keggin Polycations**

   https://doi.org/10.1002/anie.202017321  

   Shohel, Mohammad ; Bjorklund, Jennifer L. ; Smith, Jack A. ; Kravchuk, Dmytro V. ; Mason, Sara E. ; Forbes, Tori Z. ( March 2021 , Angewandte Chemie International Edition)

   Keggin‐type polyaluminum cations belong to a unique class of compounds with their large positive charge, hydroxo bridges, and divergent isomerization/oligomerization. Previous reports indicated that oligomerization of this species can only occur through one isomer (δ), but herein we report the isolation of largest Keggin‐type cluster that occurs through self‐condensation of four ϵ‐isomers ϵ‐GeAl₁₂⁸⁺to form [Ge₄O₁₆Al₄₈(OH)₁₀₈(H₂O)₂₄]²⁰⁺cluster (Ge₄Al₄₈). The cluster was crystallized and structurally characterized by single‐crystal X‐ray diffraction (SCXRD) and the elemental composition was confirmed by ICP‐MS and SEM‐EDS. Additional dynamic light scattering experiments confirms the presence of theGe₄Al₄₈in thermally aged solutions. DFT calculations reveal that a single atom Ge substitution in tetrahedral site of ϵ‐isomer is the key for the formation ofGe₄Al₄₈because it activates deprotonation at key surface sites that control the self‐condensation process.

    

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3. Structure and Bonding in [Sb@In 8 Sb 12 ] 3− and [Sb@In 8 Sb 12 ] 5−

   https://doi.org/10.1002/anie.201904109  

   Liu, Chao ; Tkachenko, Nikolay V. ; Popov, Ivan A. ; Fedik, Nikita ; Min, Xue ; Xu, Cong-Qiao ; Li, Jun ; McGrady, John E. ; Boldyrev, Alexander I. ; Sun, Zhong-Ming ( June 2019 , Angewandte Chemie International Edition)
4. The non-covalently bound SO⋯H 2 O system, including an interpretation of the differences between SO⋯H 2 O and O 2 ⋯H 2 O

   https://doi.org/10.1039/C8CP05749D  

   Misiewicz, Jonathon P. ; Noonan, Julia A. ; Turney, Justin M. ; Schaefer, Henry F. ( November 2018 , Physical Chemistry Chemical Physics)

   Despite the interest in sulfur monoxide (SO) among astrochemists, spectroscopists, inorganic chemists, and organic chemists, its interaction with water remains largely unexplored. We report the first high level theoretical geometries for the two minimum energy complexes formed by sulfur monoxide and water, and we report energies using basis sets as large as aug-cc-pV(Q+d)Z and correlation effects through perturbative quadruple excitations. One structure of SO⋯H 2 O is hydrogen bonded and the other chalcogen bonded. The hydrogen bonded complex has an electronic energy of −2.71 kcal mol −1 and a zero kelvin enthalpy of −1.67 kcal mol −1 , while the chalcogen bonded complex has an electronic energy of −2.64 kcal mol −1 and a zero kelvin enthalpy of −2.00 kcal mol −1 . We also report the transition state between the two structures, which lies below the SO⋯H 2 O dissociation limit, with an electronic energy of −1.26 kcal mol −1 and an enthalpy of −0.81 kcal mol −1 . These features are much sharper than for the isovalent complex of O 2 and H 2 O, which only possesses one weakly bound minimum, so we further analyze the structures with open-shell SAPT0. We find that the interactions between O 2 and H 2 O are uniformly weak, but the SO⋯H 2 O complex surface is governed by the superior polarity and polarizability of SO, as well as the diffuse electron density provided by sulfur's extra valence shell. 

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5. H 2 evolution from H 2 O via O–H oxidative addition across a 9,10-diboraanthracene

   https://doi.org/10.1039/D0CC05261B  

   Taylor, Jordan W. ; Harman, W. Hill ( November 2020 , Chemical Communications)

   null (Ed.)

   The water reactivity of the boroauride complex ([Au(B 2 P 2 )][K(18-c-6)]; (B 2 P 2 , 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) and its corresponding two-electron oxidized complex, Au(B 2 P 2 )Cl, are presented. Au(B 2 P 2 )Cl is tolerant to H 2 O and forms the hydroxide complex Au(B 2 P 2 )OH in the presence of H 2 O and triethylamine. [Au(B 2 P 2 )]Cl and [Au(B 2 P 2 )]OH are poor Lewis acids as judged by the Gutmann–Becket method, with [Au(B 2 P 2 )]OH displaying facile hydroxide exchange between B atoms of the DBA ring as evidenced by variable temperature NMR spectroscopy. The reduced boroauride complex [Au(B 2 P 2 )] − reacts with 1 equivalent of H 2 O to produce a hydride/hydroxide product, [Au(B 2 P 2 )(H)(OH)] − , that rapidly evolves H 2 upon further H 2 O reaction to yield the dihydroxide compound, [Au(B 2 P 2 )(OH) 2 ] − . [Au(B 2 P 2 )]Cl can be regenerated from [Au(B 2 P 2 )(OH) 2 ] − via HCl·Et 2 O, providing a synthetic cycle for H 2 evolution from H 2 O enabled by O–H oxidative addition at a diboraanthracene unit. 

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