ChemInform Abstract: Preparation, Structure, and Properties of the Corner‐Shared Double Cubes [Mo₆HgO₈(H₂O)₁₈]⁸⁺ (Q: S, Se) and Tungsten Analogues.

Abstract

Preparation, Structure, and Properties of the Corner-Shared Double Cubes [Mo 6 HgO 8 (H 2 O) 18 ] 8+ (Q: S, Se) and Tungsten Analogues. -Corner-shared double cubes [Mo 6 HgQ 8 (H 2 O) 18 ] 8+ (Q: S, Se) are obtained by reacting Hg metal or Hg 1 2 with [Mo 3 Q 4 (H 2 O) 9 ] 4+ under air-free conditions (2 M HCl or 4 M TosOH). The reactions are monitored by UV/VIS spectrophotometry. As revealed by XRD the compounds [M 6 HgQ 8 Cl 4 (H 2 O) 14 ] (C 36 H 36 N 24 O 12 )Cl 4 ·14H 2 O (M: Mo, W) are isostructural. They have six carbonyl O atoms above and six below the ring of the cucurbituril molecule, which form hydrogen bonds to H 2 O ligands of the double cube. Four chlorides are coordinated to M, and four chlorides act as counterions. Redox properties of the title cations are reported. -(FEDIN, VLADIMIR P.; SOKOLOV, MAXIM; LAMPRECHT, GERT J.; HERNANDEZ-MOLINA, RITA; SEO, MI-SOOK; VIROVETS, ALEXANDER V.; CLEGG, WILLIAM; SYKES, A.

X-ray-Induced Photoreduction of Hg(II) in Aqueous Frozen Solution Yields Nearly Monatomic Hg(0)

“…Density Functional Theory (DFT) Calculations. DFT geometry optimizations were carried out using DMol 3 and Biovia Materials Studio, version 2017 R2 20,21 using the meta-GGA approximation employing the M11-L functional both for the potential during the self-consistent field procedure and for the energy. 22 DMol 3 double numerical basis sets included polarization functions for all atoms with all-electron relativistic core treatments.…”

“…1 The few Hg(0) complexes that have been characterized do show some common structural features. In some, Hg(0) is part of an electron-rich transition-metal-ion chalcogenide cluster 2,3 while in others Hg(0) is bound between two phosphine-coordinated Pt(0) 4 or iodide and Mo(0), 5 or it is trapped in a gold(I)-metallocryptand cage complex with two metal−metal bonds. 6 In all cases thus far reported, the Hg(0) is diffusely bound by very long and weak bonds to the coordinating atoms.…”