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1. Syntheses and crystal structures of three triphenylsulfonium salts of manganese(II), iron(III) and cobalt(II)

   https://doi.org/10.1107/S2056989025006668  

   Callaway, Waylan; Elterman, Matthew; Krasilnikov, Nikita; Roberts, Gavin; Rutan, Davis; Spencer, Ty; Padgett, Clifford W; Lynch, Will E (August 2025, Acta Crystallographica Section E Crystallographic Communications)

   Bis(triphenylsulfonium) tetrachloridomanganate(II), (C₁₈H₁₅S)₂[MnCl₄] (I), triphenylsulfonium tetrachloridoferrate(III), (C₁₈H₁₅S)[FeCl₄] (II), and bis(triphenylsulfonium) tetrachloridocobaltate(II), (C₁₈H₁₅S)₂[CoCl₄] (III), crystallize in the monoclinic space groupsP2₁/n[(I) and (III)] andP2₁/c[(II)]. Compounds (I) and (III) each contain two crystallographically independent triphenylsulfonium (TPS⁺) cations in the asymmetric unit, whereas (II) has one. In all three compounds, the sulfonium centers adopt distorted trigonal–pyramidal geometries, with S—C bond lengths falling roughly in the 1.78–1.79 Å range and C—S—C angles observed at about 101 to 106°. The [MCl₄]ⁿ⁻anions (M= Mn²⁺, Fe³⁺, Co²⁺;n= 2,1,2) adopt slightly distorted tetrahedral geometries, withM—Cl bond lengths in the 2.19–2.38 Å range and Cl—M—Cl angles of approximately 104–113°. Hirshfeld surface analyses shows that H...H and H...C contacts dominate the TPS⁺cation environments, whereas H...Cl and shortM—S interactions link each [MCl₄]ⁿ⁻anion to the surrounding cations. In (I) and (III), inversion-centered π–π stacking further consolidates the crystal packing, while in (II) no π–π interactions are observed. 

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2. Syntheses and crystal structures of three triphenylsulfonium halometallate salts of zinc, cadmium and mercury

   https://doi.org/10.1107/S2056989025002245  

   Artis, Rylan; Heyward, Elizabeth; Reyes, Naomi; Van_Ostenbridge, Kaitlyn; Lynch, Will E; Padgett, Clifford W (April 2025, Acta Crystallographica Section E Crystallographic Communications)

   Bis(triphenylsulfonium) tetrachloridozinc(II), (C₁₈H₁₅S)₂[ZnCl₄] (I), bis(triphenylsulfonium) tetrachloridocadmium(II), (C₁₈H₁₅S)₂[CdCl₄] (II), and bis(triphenylsulfonium) tetrachloridomercury(II) methanol monosolvate, (C₁₈H₁₅S)₂[HgCl₄]·CH₃OH (III), each crystallize in the monoclinic space groupP2₁/n. In all three structures, there are two crystallographically independent triphenylsulfonium (TPS) cations per asymmetric unit, each adopting a distorted trigonal–pyramidal geometry about the S atom (S—C bond lengths in the 1.77–1.80 Å range and C—S—C angles of 100–107°). The [MCl₄]^2–anions (M= Zn²⁺, Cd²⁺, Hg²⁺) are tetrahedral; their M—Cl bond lengths systematically increase from Zn²⁺to Hg²⁺, consistent with the larger ionic radius of the heavier metal. Hirshfeld surface analyses show that H...H and H...C contacts dominate the TPS cation environments, whereas H...Cl and S...Minteractions anchor each [MCl₄]^2–anion to two surrounding TPS cations. Weak C—H...Cl hydrogen bonds, as well as inversion-centered π–π stacking, generate layers in (I) and (II) and dimeric [(TPS)₂–HgCl₄]₂assemblies in (III). 

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3. Diverse Coordination Geometries Derived from Trisaminocyclohexane Ligands with Appended Outer‐Sphere Hydrogen Bond Donors

   https://doi.org/10.1002/ejic.202300434  

   Ekanayake, Danushka_M; Sheridan, Patrick_E; Lindeman, Sergey_V; Fiedler, Adam_T (September 2023, European Journal of Inorganic Chemistry)

   Abstract With the aim of constructing hydrogen‐bonding networks in synthetic complexes, two new ligands derived fromcis,cis‐1,3,5‐triaminocyclohexane (TACH) have been prepared that feature pendant pyrrole or indole rings as outer‐sphere H‐bond donors. The TACH framework offers a facial arrangement of threeN‐donors, thereby mimicking common coordination motifs in the active sites of nonheme Fe and Cu enzymes. X‐ray structural characterization of a series of Cu^I‐X complexes (X=F, Cl, Br, NCS) revealed that these neutral ligands (H₃L^R, R=pyrrole or indole) coordinate in the intended facialN₃manner, yielding four‐coordinate complexes with idealizedC₃symmetry. The N−H units of the outer‐sphere heterocycles form a hydrogen‐bonding cavity around the axial (pseudo)halide ligand, as verified by crystallographic, spectroscopic, and computational analyses. Treatment of H₃L^pyrroleand H₃L^indolewith divalent transition metal chlorides (M^IICl₂, M=Fe, Cu, Zn) causes one heterocycle to deprotonate and coordinate to the M(II) center, giving rise to tetradentate ligands with two remaining outer‐sphere H‐bond donors. Further ligand deprotonation is observed upon reaction with Ni(II) and Cu(II) salts with weakly coordinating counteranions. The reported complexes highlight the versatility of TACH‐based ligands with pendant H‐bond donors, as the resulting scaffolds can support multiple protonation states, coordination geometries, and H‐bonding interactions. 

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4. Antiferromagnetic Ordering in A One‐Dimensional Organic Copper Chloride Hybrid Insulator

   https://doi.org/10.1002/anie.202412759  

   Islam, Md_Sazedul; Comstock, Andrew; Hua, Zhenqi; Thapa, Puja; He, Yufang; Ben‐Akacha, Azza; Liu, He; Manny, Tarannuma_Ferdous; Viera, Jarek; Lin, Xinsong; et al (September 2024, Angewandte Chemie International Edition)

   Abstract Low dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under‐explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic‐copper (II) chloride hybrid (C₈H₂₂N₂)Cu₂Cl₆. Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu₂Cl₆²⁻]_∞chains, (C₈H₂₂N₂)Cu₂Cl₆is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two‐terminal (2T) electrical measurement on a (C₈H₂₂N₂)Cu₂Cl₆single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics. 

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5. A [ ¹ H, ¹⁵ N] Heteronuclear Single Quantum Coherence NMR Study of the Solution Reactivity of the Ruthenium‐Based Mitochondrial Calcium Uniporter Inhibitor Ru265

   https://doi.org/10.1002/ejic.202100995  

   Woods, Joshua_J; Spivey, Jesse_A; Wilson, Justin_J (January 2022, European Journal of Inorganic Chemistry)

   Abstract The synthesis and characterization of the¹⁵N‐labeled analogue of the mitochondrial calcium uptake inhibitor [Cl(NH₃)₄Ru(μ‐N)Ru(NH₃)₄Cl]³⁺(Ru265) bearing [¹⁵N]NH₃ligands is reported. Using [¹H,¹⁵N] HSQC NMR spectroscopy, the rate constants for the axial chlorido ligand aquation of [¹⁵N]Ru265 in pH 7.4 buffer at 25 °C were found to bek₁=(3.43±0.03)×10⁻⁴ s⁻¹andk₂=(4.03±0.09)×10⁻³ s⁻¹. The reactivity of [¹⁵N]Ru265 towards biologically relevant small molecules was also assessed via this method, revealing that this complex can form coordination bonds to anionic oxygen and sulfur donors. Time‐based studies on these ligand‐binding reactions reveal this process to be slow relative to the time required for the complex to inhibit mitochondrial calcium uptake, suggesting that hydrogen‐bonding interactions, rather than the formation of coordination bonds, may play a more significant role in mediating the inhibitory properties of this complex. 

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