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1. 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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2. D -Mannosamine hydrochloride (2-amino-2-deoxy- D -mannose hydrochloride): ionic hydrogen bonding in saccharides involving chloride and aminium ions

   https://doi.org/10.1107/S2053229622002121  

   Lin, Jieye; Oliver, Allen G.; Serianni, Anthony S. (April 2022, Acta Crystallographica Section C Structural Chemistry)

   D-Mannosamine hydrochloride (2-amino-2-deoxy-D-mannose hydrochloride), C 6 H 14 NO 5 + ·Cl − , (I), crystallized from a methanol/ethyl acetate/ n -hexane solvent mixture at room temperature in a 4 C 1 chair conformation that is slightly distorted towards the C3,O5 B form. A comparison of the structural parameters of (I) with the corresponding parameters in α-D-glucosamine hydrochloride, (II), and β-D-galactosamine hydrochloride, (III)/(III′), was undertaken to evaluate the effects of ionic hydrogen bonding on structural properties. Three types of ionic hydrogen bonds are present in the crystals of (I)–(III)/(III′), i.e. N + —H...O, N + —H...Cl − , and O—H...Cl − . The exocyclic structural parameters in (I), (II), and (III)/(III′) appear to be most influenced by this bonding, especially the exocyclic hydroxy groups, which adopt eclipsed conformations enabled by ionic hydrogen bonding to the chloride anion. Anomeric disorder was observed in crystals of (I), with an α:β ratio of 37:63. However, anomeric configuration appears to exert minimal structural effects; that is, bond lengths, bond angles, and torsion angles are essentially identical in both anomers. The observed disorder at the anomeric C atom of (I) appears to be caused by the presence of the chloride anion and atom O3 or O4 in proximal voids, which provide opportunities for hydrogen bonding to atom O1 in both axial and equatorial orientations. 

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3. Geometrical variations of two manganese(II) complexes with closely related quinoline-based tripodal ligands

   https://doi.org/10.1107/S2056989021009786  

   Frey, Steven T.; Ballot, Jasper G.; Hands, Allison; Cirka, Haley A.; Rinaolo, Katheryn C.; Phalkun, Nich N.; Kaur, Manpreet; Jasinski, Jerry P. (October 2021, Acta Crystallographica Section E Crystallographic Communications)

   Structural analyses of the compounds di-μ-acetato-κ 4 O : O ′-bis{[2-methoxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ]manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn 2 (C 23 O 2 ) 2 (C 23 H 23 N 3 O) 2 ](C 24 H 20 B)·1.45CH 2 Cl 2 or [Mn(DQMEA)(μ-OAc) 2 Mn(DQMEA)](BPh 4 ) 2 ·1.45CH 2 Cl 2 or [1] (BPh 4 ) 2 ·1.45CH 2 Cl 2 , and (acetato-κ O )[2-hydroxy- N , N -bis(quinolin-2-ylmethyl)ethanamine-κ 4 N , N ′, N ′′, O ](methanol-κ O )manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH 3 COO)(C 22 H 21 N 3 O)(CH 3 OH)](C 24 H 20 B)·CH 3 OH or [Mn(DQEA)(OAc)(CH 3 OH)]BPh 4 ·CH 3 OH or [2] BPh 4 ·CH 3 OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to Mn II ions. In the asymmetric unit, compound [1] (BPh 4 ) 2 ·(CH 2 Cl 2 ) 1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric Mn II centers have a distorted, octahedral geometry in which the quinoline nitrogen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each Mn II center, a coordinated acetate oxygen participates in C—H...O hydrogen-bonding interactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π – π stacking interactions and intermolecular cation–anion interactions stabilize the crystal packing. In the asymmetric unit, compound [2] BPh 4 ·CH 3 OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitrogen, the nitrogen atom of each quinoline group, and the alcohol oxygen of the tetradentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the Mn II center in [2] BPh 4 ·CH 3 OH is also a distorted octahedron, but the quinoline nitrogen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O—H...O) and quinolyl (C—H...O and N—H...O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of intermolecular O3—H3...O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and intermolecular cation–anion interactions contribute to the crystal packing. 

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4. Synthesis, Reductive Reactivity and Anticancer Activity of Cobalt(III)– and Manganese(III)–Salen Complexes

   https://doi.org/10.3390/chemistry7030085  

   Kanina, Amy; Mei, Haiyu; Palma, Cheska; Neary, Michelle C; Cheng, Shu-Yuan; Zhang, Guoqi (June 2025, Chemistry)

   Mn(III)– and Co(III)–salen complexes (Mn-1 and Co-2) have been synthesized by a simple one-pot procedure through oxidation of Mn(II) and Co(II) precursors in air. X-ray structural analysis reveals that both complexes adopt similar coordination modes, including a typical square planar metal/salen coordination sphere, which is further occupied by two axial ligands, i.e., an acetate anion and a water molecule. Despite their structural similarity, they are not isomorphous given their distinct cell parameters. In the solid-state structures, both complexes exist as hydrogen-bonded dimers through hydrogen bonding interactions between the axially coordinating water molecules and outer O4 cavity from another molecule of the complex. The reductive activity of both complexes has been explored. While the reaction of Mn-1 with potassium triethylborohydride was unsuccessful, leading to a complicated mixture, the use of Co-2 furnished the formation of a novel product (CoK-3) that was isolated as red crystals in reasonable yield. CoK-3 was characterized as a heterometallic dimer involving the coordination of a K+ ion within the O4 cavity of a semi-hydrogenated salen/cobalt complex while the cobalt center has been reduced from Co(III) to Co(II). In addition, an attempt at reducing Co-2 with pinacolborane resulted in the isolation of crystals of Co-4, whose structure was determined as a simple square planar CoII–salen complex. Finally, three complexes (Mn-1, Co-2 and CoK-3) have been investigated for their cytotoxic activities against two human breast cancer cell lines (MCF-7 and MDA-MB 468) and a normal breast epitheliel cell line (MCF-10A), with cisplatin used as a reference in order to discover potential drug candidates that may compete with cisplatin. The results reveal that Co-2 can be a promising drug candidate, specifically for the MCF-7 cancer cells, with minimal damage to healthy cells. 

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5. Is the Chemisorbed CO ₂ in Ionic Liquid Electrolytes Active for Electrochemical Utilization? A Case Study on Carboxylate and Carbamate Speciation

   https://doi.org/10.1149/1945-7111/addf83  

   Coskun, Oguz_Kagan; Dongare, Saudagar; Gurkan, Burcu (June 2025, Journal of The Electrochemical Society)

   Abstract This study examines the activity of chemisorbed CO2 species in the microenvironment formed by bifunctional ionic liquids (ILs) in the reactive capture and conversion (RCC) of CO2 to CO on silver. Comparative electroanalytical measurements with imidazolium based ILs were performed to probe the impact of electrostatic interactions, anion and cation basicity, and hydrogen bonding on RCC. Particularly, ILs with 1-ethyl,3-methylimidazolium ([EMIM]+) and 1-ethyl, 2,3-methylimidazolium ([EMMIM]+) cations and aprotic heterocyclic anions of 2-cyanopyrrolide ([2-CNpyr]) and 1,2,4-triazolide ([1,2,4-Triz]) were examined for RCC. It was found that anion–CO2 carbamate complexes facilitate RCC at significantly lower overpotentials compared to cation–CO2 carboxylate complexes. Additionally, [EMIM]+ was found to better stabilize anion–CO2 complexes than [EMMIM]+. Furthermore, it was found that 2-CNpyrH that naturally forms in CO2 absorption competes for electrode surface adsorption with the anion–CO2 carbamate complex, thereby reducing the electrochemical activity of the anion–CO2 complex. These results highlight the importance of IL structure in tuning the interfacial interactions and suggest that ILs with anion-dominated CO2 chemisorption enhances CO2 utilization in RCC applications. 

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