Pinpointing the Cl Coordination Effect on Mn-N3-Cl Moiety Toward Boosting Reaction Kinetics and Suppressing Shuttle Effect in Li-S Batteries.

Single atom catalysts (SACs) are highly favored in Li-S batteries due to their excellent performance in promoting the conversion of lithium polysulfides (LiPSs) and inhibiting their shuttling. However, the intricate and interrelated microstructures pose a challenge in deciphering the correlation between the chemical environment surrounding the active site and its catalytic activity. Here, a novel SAC featuring a distinctive Mn-N3-Cl moiety anchored on B, N co-doped carbon nanotubes (MnN3Cl@BNC) is synthesized. Subsequently, the selective removal of the Cl ligands while inheriting other microstructures is performed to elucidate the effect of Cl coordination on catalytic activity. The Cl coordination effectively enhances the electron cloud density of the Mn-N3-Cl moiety, reducing the band gap and increasing the adsorption capacity and redox kinetics of LiPSs. As a modified separator for Li-S batteries, MnN3Cl@BNC exhibits high capacities of 1384.1 and 743 mAh g-1 at 0.1 and 3C, with a decay rate of only 0.06% per cycle over 700 cycles at 1 C, which is much better than that of MnN3OH@BNC. This study reveals that Cl coordination positively contributes to improving the catalytic activity of the Mn-N3-Cl moiety, providing a fresh perspective for the design of high-performance SACs.

A Monometallic Bis(cyaphido) Complex.

The first example of a bis(cyaphido) complex, trans-[Ru(dppe)2(C≡P)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand. Synthesis is achieved from the precedent cation [Ru(dppe)2(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans-[Ru(dppe)2(C≡N)(C≡P)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart. This demonstrates an enhanced π-acidity for -C≡P over -C≡N, while computational studies reveal also a higher π-donor character for the cyaphido ligand.

Phosphonium-substituted Diphosphaindenylide (PPI): Exploration of Biradical Character and Ligand Properties.

Starting from C6 H4 (PCl2 )2 and the TMS-substituted ylide (TMS)2 C=PR3 (TMS=trimethylsilyl, R=p-tolyl), the phosphonium-substituted diphosphaindenylide PPI was prepared in two steps. CASSCF calculations as well as the reactivity toward diphenyl acetylene suggest a notable biradical character in PPI. Reaction with [Cr(CO)3 (MeCN)3 ] affords the complex [Cr(CO)3 (η5 -PPI)] (5). This complex was employed to explore the ligand properties of PPI, which demonstrates considerable potential through the combination of strong metal-ligand interactions and the possibility of a pronounced indenyl effect.

An Unusual Macrocyclic Hexamer of an Iso-Tellurazole N-Oxide Featuring CTe O Chalcogen Bonds is Formed by κ6 -O Complexation to Fe(II) and Ni(II).

Studies of the supramolecular chemistry of iso-tellurazole N-oxides have been confined to non-polar media until now. To overcome that limitation, an iso-tellurazole N-oxide was derivatized with a primary alcohol group; the compound is soluble in polar solvents and stable in acidic to neutral aqueous media. Nickel (II) and iron (II) form macrocyclic complexes with six molecules of that iso-tellurazole N-oxide in a hitherto not-observed macrocyclic arrangement defined by CTe⋅⋅⋅O chalcogen bonds and κ6 -O bound to the metal ion. This behaviour is in sharp contrast with the κn -Te (n=1,2,4) complexes formed by soft metal ions.

Chemoselective Post-Synthesis Modification of Pyridyl-Substituted, Aromatic Phosphorus Heterocycles: Cationic Ligands for Coordination Chemistry.

Triazaphospholes are potential polydentate ligands due to the presence of both phosphorus and nitrogen donor atoms within the aromatic 5-membered heterocycle. The incorporation of an additional pyridyl-substituent opens up the possibility of a post-synthesis modification via chemoselective and also stepwise alkylation exclusively of the nitrogen atoms. This can be controlled by the choice and by the stoichiometry of the electrophile and allows the targeted synthesis of a variety of novel mono- and dicationic ligands. Reaction with Cu(I)-halides causes the formation of cuprates of the type [CuXn](n-1)-, which enables coordination of the π-acidic phosphorus donor to the negatively charged metal core, which is favored over the coordination by a strongly σ-donating nitrogen atom. The use of cationic triazaphosphole derivatives can be used as a strategy to enforce the coordination of the ligand to an electron rich metal solely via the phosphorus atom. However, there is a subtle balance between the formation of either coordination polymers or dimeric structures, as the substitution pattern on the heterocycle and the nature of the halide have a large influence on the coordination motifs formed.

Azophosphines: Synthesis, Structure and Coordination Chemistry.

The conceptual replacement of nitrogen with phosphorus in common organic functional groups unlocks new properties and reactivity. The phosphorus-containing analogues of triazenes are underexplored but offer great potential as flexible and small bite-angle ligands. This manuscript explores the synthesis and characterisation of a family of air-stable azophosphine-borane complexes, and their subsequent deprotection to the free azophosphines. These compounds are structurally characterised, both experimentally and computationally, and highlight the availability of the phosphorus lone pair for coordination. This is confirmed by demonstrating that neutral azophosphines can act as ligands in Ru complexes, and can coordinate as monodentate or bidentate ligands in a controlled manner, in contrast to their nitrogen analogues.

Nitrogen Fixation by Manganese Complexes - Waiting for the Rush?

Manganese is currently experiencing a great deal of attention in homogeneous catalysis as a sustainable alternative to platinum group metals due to its abundance, affordable price and low toxicity. While homogeneous nitrogen fixation employing well-defined transition metal complexes has been an important part of coordination chemistry, manganese derivatives have been only sporadically used in this research area. In this contribution, the authors systematically cover manganese organometallic chemistry related to N2 activation spanning almost 60 years, identify apparent pitfalls and outline encouraging perspectives for its future development.

Selective Manipulation of Well-Defined Trinuclear Pd(II)-Complexes.

Several strategies are available to design well-defined multimetallic molecular entities bearing functional ligands. Substoichiometric exchange reactions in the coordination sphere of pre-existing multinuclear precursors are relatively underexploited in this context. Palladium(II) acetate is not a mononuclear compound in the solid state but rather exists as a trimer, i. e. [Pd3(OAc)6]. Although this material is ubiquitously used to synthesize mononuclear Pd species, it may principally also lend itself to selective exchange of some of the edge-sharing acetate units in its triangular motif, whilst keeping the overall multinuclear architecture intact. Strikingly, little is known about the controlled manipulation and substoichiometric substitution chemistry of this well-defined conglomerate. We herein conclusively demonstrate that, for the first time, the targeted exchange of two or four acetate units from the Pd3(acetate)6 platform is possible, thereby installing either one or two new tridentate ligands onto this trinuclear architecture. Follow-up exchange and substitution chemistry is available without disrupting the multimetallic nature of the core structure. New complexes 2-7 are all conclusively characterized using multinuclear NMR spectroscopy, UV-vis and IR spectroscopy as well as X-ray diffraction analysis.

Stability of the Protactinium(V) Mono-Oxo Cation Probed by First-Principle Calculations.

This study explores the distinctive behavior of protactinium (Z=91) within the actinide series. In contrast to neighboring elements like uranium or plutonium, protactinium in the pentavalent state diverges by not forming the typical dioxo protactinyl moiety PaO2 + in aqueous phase. Instead, it manifests as a monooxo PaO3+ cation or a Pa5+ . Employing first-principle calculations with implicit and explicit solvation, we investigate two stoichiometrically equivalent neutral complexes: PaO(OH)2 (X)(H2 O) and Pa(OH)4 (X), where X represents various monodentate and bidentate ligands. Calculating the Gibbs free energy for the reaction PaO(OH)2 (X)(H2 O)→Pa(OH)4 (X), we find that the PaO(OH)2 (X)(H2 O) complex is stabilized with Cl- , Br- , I- , NCS- , NO3 - , and SO4 2- ligands, while it is not favored with OH- , F- , and C2 O4 2- ligands. Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Orbital (NBO) methods reveal the Pa mono-oxo bond as a triple bond, with significant contributions from the 5f and 6d shells. Covalency of the Pa mono-oxo bond increases with certain ligands, such as Cl- , Br- , I- , NCS- , and NO3 - . These findings elucidate protactinium's unique chemical attributes and provide insights into the conditions supporting the stability of relevant complexes.

7Li NMR Spectroscopy: A Tool for Determining Dimerization Constants and Averaged Dimerization Constants of the Monomer/Dimer Equilibrium of Hierarchical Helicates.

7Li nuclear magnetic resonance (NMR) spectroscopy is an ideal tool to study hierarchically assembled helicates of the form Li[Li3L6Ti2]. Internally bound and external lithium ions can be well distinguished by solution- or solid-state NMR spectroscopy and dimerization constants of the monomer/dimer equilibrium can be easily determined in solution. Averaged dimerization constants can be estimated in case of statistical mixtures of helicates formed from mixtures of ligands.

Recent Developments of Dual Single-Atom Catalysts for Nitrogen Reduction Reaction.

Ammonia is vital for fertilizer production, hydrogen storage, and alternative fuels. The conventional Haber-Bosch process for ammonia production is energy-intensive and environmentally harmful. Designing environmentally friendly and low-energy consumption strategies for electrocatalytic N2 reduction reaction (ENRR) in mild conditions is meaningful. Single-atom catalysts (SACs) have been studied extensively for NRR due to their high atomic utilization and unique electronic structure but are limited by their poor faradic efficiency and low ammonia formation yield. Dual single-atom catalysts (DSACs) have recently emerged as a promising solution for the effective activation of molecular N2 , providing diverse active sites and synergistic interactions between adjacent atoms. In this review, we summarize the latest advances in metal DSACs for electrochemical ENRR based on both theoretical calculations and experimental studies, including aspects such as their variety, coordination, support, N2 adsorption and activity mechanisms, the characterization of NRR and electrochemical cell Configuration. We also address challenges and prospects in this rapidly evolving field, providing a comprehensive overview of DSACs for ENRR.

Modulating the Coordination Chemistry of Cobalt Catalytic Sites by Ruthenium Species to Accelerate the Polysulfide Conversion Kinetics in Lithium-Sulfur Batteries.

The performance of lithium-sulfur batteries is compromised by the loss of sulfur as dissolved polysulfides in the electrolyte and consequently the polysulfide redox shutting effect. Accelerating the conversion kinetics of polysulfide intermediates into sulfur or lithium sulfide through electrocatalysis has emerged as a root-cause solution. Co-N-C composite electrocatalyst is commonly used for this purpose. It is illustrated here that how the effectiveness can be improved by modulating the coordination chemistry of Co-N-C catalytic sites through introducing Ru species (RuCo-NC). The well-dispersed Ru in the Co-NC carbon matrix altered the total charge distribution over the Co-N-C catalytic sites and led to the formation of electron-rich Co-N, which is highly active for the polysulfide conversion reactions. Using Ru to modulate the electronic structure in the Co-N-C configuration and the additional catalytic sites over the Ru-Nx species can manifest optimal adsorption behavior of polysulfides. Consequently, the sulfur cathode with RuCo-NC can reduce the capacity fade rate from 0.11 % per cycle without catalyst (initial capacity of 701 mAh g-1) to 0.054 % per cycle (initial capacity of 1074 mAh g-1) over 400 cycles at 0.2 C rate. The results of this study provide the evidence for a feasible catalyst modification strategy for the polysulfide electrocatalysis.

Reversible Restrain and Release of the Dynamic Valence Isomerization in a Shape-shifting Bullvalene by Complex Formation.

In search for structural features that enable the control of the valence isomerization of the fluxional bullvalene, a bullvalene-bis(harmane) conjugate is identified that acts as chelating ligand in complexes with metal ions. Spectrometric titrations show that this ligand forms 1 : 1 complexes with Ag+, Cu+, Cu2+, and Zn2+. Most importantly, detailed NMR-spectroscopic analysis at different temperatures reveals that the complexation with Ag+ strongly affects the dynamic isomerization of the bullvalene unit of the ligand such that only one predominant valence isomer is formed, even at 5 °C. Detailed 1H-NMR-spectroscopic studies disclose an increased barrier (~11 kJ mol-1) of the Cope rearrangement. Furthermore, the addition of hexacyclene displaces the Ag+ from the complex, so that the valence isomerization is accelerated and an equilibrium with two predominant isomers is formed. In turn, repeated addition of Ag+ regains the complex with the restrained isomerization of the bullvalene unit. This method to control the valence isomerism by straightforward chemical stimuli may be used to simplify structural analysis at elevated temperatures, i. e. a feature not available so far with bullvalenes, and it may be employed as functional element in dynamic supramolecular assemblies.

Dynamics and Coordination of a P2N2 Ligand - from Twisted Conformation to Chelation.

Based on their general spacial flexibility, their Lewis and Brønsted basicity, and ability to mimic second sphere effects the 1,5-diaza-3,7-diphosphacyclooctane ligand family and their complexes have regained substantial scientific interest. It was now possible to structurally analyze a recently reported member of this family with p-tolyl and t-butyl substituents on P and N, respectively, (P2 p-tolN2 tBu). Notably, the ligand crystallizes with a 'twisted' backbone. This compound is the very first of its kind to have been unambiguously characterized with regard to its chemical and molecular structure as being in this conformation. A temperature-dependent NMR study provides insight into the molecular dynamics of two isomers in solution, which are most likely also both twisted, as judged by the observed limited reactivity. Despite the in principle unfavorable conformation of the free ligand, it was successfully chelated to tungsten and molybdenum centers in mononuclear carbonyl complexes. The ligand, a derivative thereof and four new complexes were comprehensively characterized and analyzed in comparison. This includes single crystal XRD molecular structures of P2 p-tolN2 tBu and all four complexes. P2 p-tolN2 tBu, regardless of its twisted conformation, is able to coordinate to metal centers given that enough energy (heat) for a conformational change is provided.

Improved Bipolar Properties of Ester-Functionalized Discotic Diimine-Dithiolene Complexes.

A series of platinum diimine-dithiolene complexes with a 5,6-dihydro-1,4-dithiin-2,3-dithiolato (dddt2- ) dithiolene ligand and a bipyridine carrying tris-alkoxyphenyl fragments connected through an ester linker (bpyCn, n=8, 12, 16, 10(s), 20) (Scheme 1) has been developed. The mesomorphic properties of the ligands and of the platinum complexes have been investigated by a combination of DSC, POM and SAXS analyses. The platinum complexes were found to self-organize into columnar mesophases of hexagonal symmetry over large temperature range including room temperature. Their electronic properties were also characterized by a combination of electrochemistry, absorption and emission spectroscopy measurements and TD-DFT calculations. Besides being liquid crystalline, these compounds can undergo two oxidation processes and two reduction processes in a fully reversible manner, allowing the isolation of stable dicationic and dianionic species. Such a behavior is highly promising for the development of ambipolar semiconducting soft materials.

Hydrothermally Stimulated Molecular Interfaces for Augmented Electron Delocalization in Wet-Chemical Phosphorus Recovery from Incineration Ash of Sewage Sludge.

Wet-chemically recovering phosphorus (P) from sewage sludge incineration ash (SSIA) has already become a global initiative to address P deficit, but effectively isolating P from these accompanying metals (AMs) through adsorption in a SSIA-derived extract remains elusive. Here, we devised a hydrothermal stimulus-motivated thermodynamic and kinetic enhancement to gain anionic ethylenediaminetetraacetic acid (EDTA) molecular interfaces for AM enclosure to resolve this conundrum. A new dosage rule based on the EDTA coordination ratio with AMs was established for the first time. Upon hydrothermal extraction at 140 °C for 1 h, the P extraction efficiency reached 96.7% or higher for these obtained SSIA samples, and then exceptional P sequestration from these EDTA-chelated AMs was realized by the peculiar lanthanum (La)-based nanoadsorbent (having 188.86 mg P/g adsorbent at pH ∼ 3.0). Relevant theoretical calculations unraveled that these delocalized electrons of tetravalent EDTA molecules boosted the enclosure of liberated AMs, thereby entailing a substantially increased negative adsorption energy (-408.7 kcal/mol) of P in the form of H2PO4- through intruding lattice-edged carbonates to coordinate La with monodentate mononuclear over LaCO5(1 0 1). This work highlights the prospect of molecular adaptation of these common extractants in wet-chemical P recovery from various P-included wastes, further sustaining global P circularity.

Orchestrated Cytosolic Delivery of Antigen and Adjuvant by Manganese Ion-Coordinated Nanovaccine for Enhanced Cancer Immunotherapy.

Cancer vaccines have received tremendous attention in cancer immunotherapy due to their capability to induce a tumor-specific immune response. However, their effectiveness is compromised by the insufficient spatiotemporal delivery of antigens and adjuvants in the subcellular level to induce a robust CD8+ T cell response. Herein, a cancer nanovaccine G5-pBA/OVA@Mn is prepared through multiple interactions of manganese ions (Mn2+), benzoic acid (BA)-modified fifth generation polyamidoamine (G5-PAMAM) dendrimer, and the model protein antigen ovalbumin (OVA). In the nanovaccine, Mn2+ not only exerts a structural function to assist OVA loading as well as its endosomal escape, but works as an adjuvant of stimulator of interferon genes (STING) pathway. These collaboratively facilitate the orchestrated codelivery of OVA antigen and Mn2+ into cell cytoplasm. Vaccination with G5-pBA/OVA@Mn not only shows a prophylactic effect, but also significantly inhibits growth against B16-OVA tumors, indicating its great potential for cancer immunotherapy.

[Fe(µ2-OH)6]3- Linked Fe3O Triads: Mössbauer Evidence for Trigonal µ3-O2- or µ3-OH- Groups in Bridged versus Unbridged Complexes.

The syntheses, coordination chemistry, and Mössbauer spectroscopy of hepta-iron(III) complexes using derivatised salicylaldoxime ligands from two categories; namely, 'single-headed' (H2L) and 'double-headed' (H4L) salicylaldoximes are described. All compounds presented here share a [Fe3-µ3-O] core in which the iron(III) ions are µ3-hydroxo-bridged in the complex C1 and µ3-oxo-bridged in C2 and C3. Each compound consists of 2 × [Fe3-µ3-O] triads that are linked via a central [Fe(µ2-OH)6]3- ion. In addition to the charge balance and microanalytical evidence, Mössbauer measurements support the fact that the triads in C1 are µ3-OH bridged and are µ3-O bridged in C2 and C3.

Monofluorophos-Metal Complexes: Ripe for Future Discoveries in Homogeneous Catalysis.

The discovery that cyclic (ArO)2PF can support Rh-catalysts for hydroformylation with significant advantages in tuning regioselectivity transformed the study of metal complexes of monofluorophos ligands from one of primarily academic interest to one with potentially important applications in catalysis. In this review, the syntheses of monofluorophosphites, (RO)2PF, and monofluorophosphines, R2PF, are discussed and the factors that control the kinetic stability of these ligands to hydrolysis and disproportionation are set out. A survey of the coordination chemistry of these two classes of monofluorophos ligands with d-block metals is presented, emphasising the bonding of the fluorophos to d-block metals, predominantly in low oxidation states. The application of monofluorophos ligands in homogeneous catalysis (especially hydroformylation and hydrocyanation) is discussed, and it is argued that there is great potential for monofluorophos complexes in future catalytic applications.

Reactions of Cadmium(II) Halides and Di-2-Pyridyl Ketone Oxime: One-Dimensional Coordination Polymers.

The coordination chemistry of 2-pyridyl ketoximes continues to attract the interest of many inorganic chemistry groups around the world for a variety of reasons. Cadmium(II) complexes of such ligands have provided models of solvent extraction of this toxic metal ion from aqueous environments using 2-pyridyl ketoxime extractants. Di-2-pyridyl ketone oxime (dpkoxH) is a unique member of this family of ligands because its substituent on the oxime carbon bears another potential donor site, i.e., a second 2-pyridyl group. The goal of this study was to investigate the reactions of cadmium(II) halides and dpkoxH in order to assess the structural role (if any) of the halogeno ligand and compare the products with their zinc(II) analogs. The synthetic studies provided access to complexes {[CdCl2(dpkoxH)∙2H2O]}n (1∙2H2O), {[CdBr2(dpkoxH)]}n (2) and {[CdI2(dpkoxH)]}n (3) in 50-60% yields. The structures of the complexes were determined by single-crystal X-ray crystallography. The compounds consist of structurally similar 1D zigzag chains, but only 2 and 3 are strictly isomorphous. Neighboring CdII atoms are alternately doubly bridged by halogeno and dpkoxH ligands, the latter adopting the η1:η1:η1:µ (or 2.0111 using Harris notation) coordination mode. A terminal halogeno group completes distorted octahedral coordination at each metal ion, and the coordination sphere of the CdII atoms is {CdII(η1 - X)(µ - X)2(Npyridyl)2(Noxime)} (X = Cl, Br, I). The trans-donor-atom pairs in 1∙2H2O are Clterminal/Noxime and two Clbridging/Npyridyl; on the contrary, these donor-atom pairs are Xterminal/Npyridyl, Xbridging/Noxime, and Xbridging/Npyridyl (X = Br, I). There are intrachain H-bonding interactions in the structures. The packing of the chains in 1∙2H2O is achieved via π-π stacking interactions, while the 3D architecture of the isomorphous 2 and 3 is built via C-H∙∙∙Cg (Cg is the centroid of one pyridyl ring) and π-π overlaps. The molecular structures of 1∙2H2O and 2 are different compared with their [ZnX2(dpkoxH)] (X = Cl, Br) analogs. The polymeric compounds were characterized by IR and Raman spectroscopies in the solid state, and the data were interpreted in terms of the known molecular structures. The solid-state structures of the complexes are not retained in DMSO, as proven via NMR (1H, 13C, and 113Cd NMR) spectroscopy and molar conductivity data. The complexes completely release the coordinated dpkoxH molecule, and the dominant species in solution seem to be [Cd(DMSO)6]2+ in the case of the chloro and bromo complexes and [CdI2(DMSO)4].