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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Trickier than It Looks: Isomerization between Five- and Six-Coordinated Zinc in Heterometallic Li 2 Zn 2 Molecule

This report describes the synthesis and characterization of two hetero bi metallic Li–Zn coordination isomers [Li 2 Zn 2 (tbaoac) 6 ] (tbaoac = tert -butyl acetoacetato) that have been isolated separately by the same stoichiometric reaction run in different organic solvents. The 6-coordinated zinc isomer ( 6-Zn ) was synthesized in acetone with high yield, while the 5-coordinated one ( 5-Zn ) was readily obtained from ethanol. The 5-Zn isomer has a low solubility in organic solvents such as alkanes and haloalkanes, while its 6-Zn counterpart exhibits a good solubility in almost all common solvents. Two isomeric molecules feature similar centrosymmetric tetranuclear cyclic assemblies, which are different in their arrangement of tbaoac ligands. While all ligands act as μ 2 -type in the structure of 5-Zn , the two tbaoac groups chelating Li appear as μ 3 -type in 6-Zn , thus providing an additional coordination for Zn ions. However, the real structural transformation between these isomers was shown to be more complex than simply making or breaking a couple of Zn–O bonds. X-ray single-crystal structure analysis, powder X-ray diffraction, multinuclear NMR, DART mass spectrometry, ICP-OES analysis, and TGA have been employed for the characterization of the isomers. The combination of powder X-ray diffraction and 1 H NMR investigation revealed that 6-Zn isomer can be quantitatively transformed to 5-Zn in ethanol, while the reverse conversion instantly takes place in acetone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Heteroleptic Four-Coordinate Tris(oxazolinyl)borato Iron(II) Compounds

The reaction of FeBr 2 and 1 equiv of thallium tris(4,4-dimethyl-2-oxazolinyl)phenylborate (TlTo M ) in THF provides To M FeBr ( 1 ), whereas FeBr 2 and 2 equiv of TlTo M react to give (To M ) 2 Fe ( 2 ). Two ν CN bands at 1604 and 1548 cm –1 suggested bidentate coordination of To M to iron in 2 . Homoleptic 2 and FeBr 2 react in THF overnight through an unusual ligand exchange process to give compound 1 , which is apparently the thermodynamic product. The salt metathesis reaction of 1 and KCH 2 Ph affords To M FeCH 2 Ph ( 3 ). The effective magnetic moments of compounds 1–3 range from 4.9 to 5.4 μ B , and these values are consistent with high-spin iron(II) (S = 2). A single 1 H NMR signal assigned to the methyl groups of the ToM ligand suggested tridentate coordination of the To M ligand to iron in 1 and 3 . X-ray crystallography studies of 1–3 establish their structure as four-coordinated tetrahedral iron complexes. To M FeBn and CO (1 atm) react to afford isolable To M Fe{C(=O)Bn}(CO) 2 ( 4 ) as a yellow solid. Complex 4 is diamagnetic (S = 0), and the three distinct methyl signals in the 1 H NMR spectrum are consistent with a six-coordinate, C s -symmetric species. This assignment is supported by its IR spectrum, which revealed intense bands at 2004 and 1935 cm –1 (symmetric and asymmetric ν CO ), at 1680 and 1662 cm –1 (acyl rotamers, ν CO ), and at 1593 and 1553 cm –1 (ν CN ) and is confirmed by a single-crystal X-ray diffraction study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Complexation of Light Trivalent Lanthanides with N-(2-Hydroxyethyl)ethylenediamine-N,N',N'-triacetic Acid in Aqueous Solutions: Thermodynamic Analysis and Coordination Modes

N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA, denoted as H 3 L) is a strong chelating ligand that is widely used in separation of f-elements as relevant to the nuclear fuel cycle. There is much to be known about the structure and composition of the coordination sphere of the complexes of HEDTA with lanthanides. The complexation of HEDTA with light lanthanides (La 3+ , Nd 3+ and Eu 3+ ) was investigated thermodynamically and structurally in aqueous solutions. Potentiometry and microcalorimetry were performed to acquire the complexation constants (25-70°C) and enthalpies (25°C), respectively, at I = 1.0mol·L -1 NaClO 4 . Coordination modes of the complexes were analyzed by luminescence spectroscopy and nuclear magnetic resonance spectroscopy. The results indicate that there are two successive Ln 3+ /HEDTA complexes, LnL(aq) and Ln 2 (H -1 L) 2 2- (Ln 3+ referred to La 3+ , Nd 3+ and Eu 3+ ; H -1 L 4- referred to the deprotonation of the hydroxyl group) during the titration. The hydroxyl group of HEDTA is coordinated in Ln 3+ /HEDTA complex. The dinuclear Ln 2 (H -1 L) 2 2- complex is present as a carboxyl-bridged centrosymmetric dimer, and two carboxyl groups in bridging positions are coordinated to two adjacent Ln 3+ cations. Complexation of the NdL(aq) is exothermic, while formation of the hydrolytic complex Nd 2 (H -1 L) 2 2- is endothermic. Both NdL aq and Nd 2 (H -1 L) 2 2- complexes are driven by entropic force. These data will help to predict the behavior of lanthanides in the separation process where HEDTA is used as the aqueous complexant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation

Understanding reaction mechanisms in many chemical and biological processes require application of rare event theories. In these theories, an effective choice of a reaction coordinate to describe a reaction pathway is essential. To this end, we study ion solvation in water using molecular dynamics simulations and explore the utility of coordination number (n = number of water molecules in the first solvation shell) as the reaction coordinate. Here we compute the potential of mean force (W(n)) using umbrella sampling, predicting multiple metastable n-states for both cations and anions. We find with increasing ionic size, these states become more stable and structured for cations when compared to anions. We have extended transition state theory (TST) to calculate transition rates between n-states. TST overestimates the rate constant due to solvent-induced barrier recrossings that are not accounted for. We correct the TST rates by calculating transmission coefficients using the reactive flux method. This approach enables a new way of understanding rare events involving coordination complexes. We gratefully acknowledge Liem Dang and Panos Stinis for useful discussion. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.

Roy, Santanu↗
DOE OSTI2024

Quantifying the Correlation between Coordination Chemistry, Interfacial Formation, and Electrochemical Performances for Mg Battery Electrolytes

Here, the rise of magnesium batteries as promising post-Li-ion energy storage technologies has sparked considerable attention toward understanding the fundamental aspects of coordination chemistry concerning Mg cations in multivalent electrolytes. This exploration includes investigating how coordination influences crucial electrolyte properties like solubility, electroreduction stability, and the formation of the interphase, all of which are pivotal for practical battery applications. Despite recent progress in developing a few functional electrolytes, a comprehensive understanding of the solvation structure that can facilitate efficient Mg deposition performance and the formulation of general design rules based on the solvation structure is still lacking. In our study, we endeavor to establish a connection between solvent and anion interactions with Mg 2+ , interface formation, and cycling performance through a series of organic ether solvents (tetrahydrofuran, glyme, diglyme, and triglyme) and amine solvents (dimethylamine, 3-methoxypropylamine, and dimethoxyethylamine). Our findings reveal a distinct coordination trend for solvent/Mg 2+ and (Mg-TFSI):solvent across various solvents, which dictates the extent of ion pairing for TFSI salts with increasing solvent molecule size and denticity. The solvated species in the bulk electrolyte across different solvents lead to diverse interfacial chemistries with varying decomposition components. We also explore the cycling efficiency as well as Mg deposition overpotentials for different solvents. A correlation analysis was conducted to assess the interplay between the structure and performance. Lastly, we apply the insights gained from these results to tailor the relative anion/Mg 2+ coordination structures using cosolvent systems, aiming for improved cell performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Coordinatively and Spatially Coconfining High-Loading Atomic Sb in Sulfur-Rich 2D Carbon Matrix for Fast K + Diffusion and Storage

The atomically dispersed materials promise ultrafast redox kinetics for alkali-ion storage. However, their relatively low mass loading limits their application. In this work, well-dispersed Sb atoms with high-loading of 23.3 wt % anchored in sulfur-rich amorphous carbon-coated reduced graphene oxide matrix (SbSA/C) are prepared by a coordinative and spatial coconfinement methodology including freeze-casting the well-dissolved Sb-chelates (Sb-thioglycolate) within graphene oxide suspension and post heating-treatment. The reduced graphene oxide substrate features open two-dimensional spatial framework for loading atomically dispersive Sb species, and the pyrolyzed Sb-chelates would provide not only massive desirable heteroatoms (S, O) for coordinating the Sb atoms but also in situ pyrolytic carbon for further spatially separating those dispersive atoms. The coordinative and spatial coconfinement engineering also endows the SbSA/C composite with atomic-level Sb atoms against migration and agglomeration during electrochemical K-storage cycling. In situ TEM reveals the uniform potassiation behavior of the SbSA/C without obvious volume change; DFT calculation and electrochemical characterization suggest the significantly lower K-ion diffusion energy barrier. Therefore, on the basis of both the active Sb center and the coordinative heteroatom, the SbSA/C electrode delivers high fast-charging capacity, outstanding rate capability and long-lifespan performance in half/full K-ion batteries (e.g., a stable capacity of 331.3 mA h g –1 is maintained over 1100 cycles at 1.0 A g –1 for half-cell).

36 MATERIALS SCIENCE↗
DOE OSTI2013

Coordination of Copper to the Membrane-Bound Form of α-Synuclein

Aggregation of the 140 amino acid protein α-synuclein (α-syn) is linked to the development of Parkinson's disease (PD). α-Syn is a copper binding protein with potential function as a regulator of metal dependent redox activity. Epidemiological studies suggest that human exposure to excess copper increases the incidence of PD. α-Syn exists in both solution and membrane bound forms. Previous work evaluated the Cu2+ uptake for α-syn in solution and identified Met1-Asp2 and His50 as primary contributors to the coordination shell, with a dissociation constant of approximately 0.1 nM. When bound to the membrane bilayer, α-syn takes on a predominantly helical conformation, which spatially separates His50 from the protein N-terminus and is therefore incompatible with the copper coordination geometry of the solution state. Here we use circular dichroism and electron paramagnetic resonance (continuous wave and pulsed) to evaluate copper coordination to the membrane bound form of α-syn. In this molecular environment, Cu2+ binds exclusively to the protein N-terminus (Met1-Asp2) with no participation from His50. Copper does not alter the membrane bound α-syn conformation, or enhance the protein's release from the bilayer. The Cu2+ affinity is similar to that identified for solution α-syn suggesting that copper coordination is retained in the membrane. Consideration of these results suggests that copper exerts its greatest conformational affect on the solution form of α-syn and this species may therefore be precursor to PD arising from environmental copper exposure.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2021

Buffered Coordination Modulation as a Means of Controlling Crystal Morphology and Molecular Diffusion in an Anisotropic Metal-Organic Framework

We know significant advances have been made in the synthesis of chemically selective environments within metal-organic frameworks, yet materials development and industrial implementation have been hindered by the inability to predictively control crystallite size and shape. One common strategy to control crystal growth is the inclusion of coordination modulators, which are molecular species designed to compete with the linker for metal coordination during synthesis. However, these modulators can simultaneously alter the pH of the reaction solution, an effect that can also significantly influence crystal morphology. Herein, noncoordinating buffers are used to independently control reaction pH during metal-organic framework synthesis, enabling direct interrogation of the role of the coordinating species on crystal growth. We demonstrate the efficacy of this strategy in the synthesis of low-dispersity single-crystals of the framework Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) in a pH 7-buffered solution using cobalt(II) acetate as the metal source. Density functional theory calculations reveal that acetate competitively binds to Co during crystallization, and by using a series of cobalt(II) salts with carboxylate anions of varying coordination strength, it is possible to control crystal growth along the c -direction. Finally, we use zero length column chromatography to show that crystal morphology has a direct impact on guest diffusional path length for the industrially important hydrocarbon m -xylene. Together, these results provide molecular-level insight into the use of modulators in governing crystallite morphology and a powerful strategy for the control of molecular diffusion rates within metal-organic frameworks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Toward Improved Charge Separation through Conformational Control in Copper Coordination Complexes

The continued development of solar energy as a renewable resource necessitates the design and study of new approaches to sustaining photodriven charge separation (CS). To this end, we present a bioinspired approach in which triggered conformational changes are used to control electron transfer (ET) events. We report, photo-induced conformational rearrangements of a ligand are translated into changes in the coordination geometry and environment about a bound metal ion. Taking advantage of the differential coordination properties of Cu I and Cu II , these dynamics facilitate intramolecular ET from Cu I to the ligand to create a CS state. The synthesis and photophysical characterization of CuCl(dpaa R ) (dpaa = dipicolylaminoacetophenone, with R = H and OMe) is presented. These ligands incorporate a fluorophore into their framework that gives rise to a twisted intramolecular charge transfer (TICT) excited state. Excited state ligand twisting provides a tetragonal coordination geometry capable of capturing Cu II in the CS state when an internal ortho-OMe binding site is present (as in dpaaOMe). We employ NMR, IR, EPR, and optical spectroscopies, X-ray diffraction, and electrochemical methods to establish the ground state properties of the Cu I and Cu II complexes. We then investigate the photophysical dynamics of these Cu I complexes via time-resolved photoluminescence (TR-PL), and optical transient absorption (OTA) spectroscopies. We show that relative to controls lacking a TICT-active ligand, the lifetime of the CS state is enhanced ~1000-fold. Further, the presence of the ortho-OMe substituent greatly enhances the lifetime of the TICT* state and biases the coordination environment toward Cu II . The presence of Cu I decreases photoinduced degradation from 14 to <2% but does not result in significant quenching via ET. Factors affecting CS in these systems are discussed, laying the groundwork for our strategy toward solar energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Quantifying Outer- and Inner-Coordination Sphere Effects Using Uranium Redox Chemistry in Molten Salt Solutions

Defining the relative influence of intramolecular and intermolecular forces is a fundamental problem in chemistry that is difficult to quantify. To address this challenge, we developed a method to evaluate the relative impact of direct chemical bonding in the inner-coordination sphere vs effects from cations in the outer-coordination sphere by comparative analysis of uranium redox reactivity in various molten salts. We observed that outer-coordination sphere cations (M 1+ ) and inner-coordination sphere anions (X 1– ) both affected uranium redox reactivity, with more polarizing M 1+ and larger X 1– favoring uranium in low oxidation states. Changing M 1+ (Li, Na, K) shifted the U IV + e 1– ⇌ U III (U IV/III ) and U III + 3e 1– → U 0 metal potentials by +330 and +240 mV, respectively. Changing X 1– (Cl, Br, I) caused larger shifts of +440 mV for the U IV/III redox potential and +1060 mV for the U 0 metal deposition potential. Using Coulomb’s Law, we correlated these potentials with electrostatic interactions between UIII and the molten salt. This model provided a facile way of predicting redox chemistry within molten salts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

A new Ru complex containing the deprotonated 2,2':6',2"-terpyridine-6,6"-diphosphonic acid (H 4 tPa) and pyridine (py) of general formula [Ru II (H 3 tPa-κ-N 3 O)(py) 2 ] + , 2 + , has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2 + presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa 4– ligand. Yet, at oxidation state IV, complex 2 + becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH – group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [Ru III (tPaO-κ-N 2 O P O C )(py) 2 ] 2– , 4 2– , where tPaO 5– is the 3-(hydroxo-[2,2':6',2"-terpyridine]-6,6"-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 4 2– , has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 4 2– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOF max ) on the order of 16 000 s –1 . A mechanistic analysis complemented with DFT calculations has further been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

In situ mechanical reinforcement of polymer hydrogels via metal-coordinated crosslink mineralization

Biological organic-inorganic materials remain a popular source of inspiration for bioinspired materials design and engineering. Inspired by the self-assembling metal-reinforced mussel holdfast threads, we tested if metal-coordinate polymer networks can be utilized as simple composite scaffolds for direct in situ crosslink mineralization. Starting with aqueous solutions of polymers end-functionalized with metal-coordinating ligands of catechol or histidine, here we show that inter-molecular metal-ion coordination complexes can serve as mineral nucleation sites, whereby significant mechanical reinforcement is achieved upon nanoscale particle growth directly at the metal-coordinate network crosslink sites.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Coordination-induced O-H/N-H bond weakening by a redox non-innocent, aluminum-containing radical

Abstract Several renewable energy schemes aim to use the chemical bonds in abundant molecules like water and ammonia as energy reservoirs. Because the O-H and N-H bonds are quite strong (>100 kcal/mol), it is necessary to identify substances that dramatically weaken these bonds to facilitate proton-coupled electron transfer processes required for energy conversion. Usually this is accomplished through coordination-induced bond weakening by redox-active metals. However, coordination-induced bond weakening is difficult with earth’s most abundant metal, aluminum, because of its redox inertness under mild conditions. Here, we report a system that uses aluminum with a redox non-innocent ligand to achieve significant levels of coordination-induced bond weakening of O-H and N-H bonds. The multisite proton-coupled electron transfer manifold described here points to redox non-innocent ligands as a design element to open coordination-induced bond weakening chemistry to more elements in the periodic table.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Modulating coordinate site occupancy in high-entropy spinel electrocatalysts

High entropy spinel oxides provide a versatile platform for electrocatalysis because multiple metal cations can be incorporated into a single crystalline lattice, enabling tunable electronic structures. However, controlling how these cations distribute between tetrahedral and octahedral coordination sites remains a major challenge, limiting rational catalyst design. Here, we modulate cation coordination site occupancy between tetrahedral and octahedral sites in a Co–Fe–Cr–Mn–Ni framework by introducing a sixth cation (Zn, Ga, Mg, or Al) with distinct site preference energies. Using density functional theory, synchrotron X-ray absorption spectroscopy, and magnetic circular dichroism, we demonstrate that Zn preferentially occupies tetrahedral sites, driving increased octahedral occupancy of cobalt. This redistribution increases the population of octahedrally coordinated cobalt in mixed oxidation states, enhances electrical conductivity, and improves oxygen evolution reaction activity. Our findings establish coordination site occupancy as a critical design parameter, providing a strategic pathway for tailoring multicomponent spinel electrocatalysts with optimized performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, this presents a new route for controlling anion transfer in electrochemically-driven separation applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Bimetallic nickel-lutetium complexes: tuning the properties and catalytic hydrogenation activity of the Ni site by varying the Lu coordination environment

We present three heterobimetallic complexes containing an isostructural nickel center and a lutetium ion in varying coordination environments. The bidentate i Pr 2 PCH 2 NHPh and nonadentate ( i Pr 2 PCH 2 NHAr) 3 tacn ligands were used to prepare the Lu metalloligands, Lu( i Pr 2 PCH 2 NPh) 3 (1) and Lu{( i Pr 2 PCH 2 NAr) 3 tacn} (2), respectively. Reaction of Ni(COD) 2 (where COD is 1,5-cyclooctadiene) and 1 afforded NiLu( i Pr 2 PCH 2 NPh) 3 (3), with a Lu coordination number (CN) of 4 and a Ni–Lu distance, d(Ni–Lu), of 2.4644(2) Å. Complex 3 can further bind THF to form 3-THF, increasing both the Lu CN to 5 and d(Ni–Lu) to 2.5989(4) Å. On the other hand, incorporation of Ni(0) into 2 provides NiLu{( i Pr 2 PCH 2 NAr) 3 tacn} (4), in which the Lu coordination environment is more saturated (CN = 6), and the d(Ni–Lu) is substantially elongated at 2.9771(5) Å. Cyclic voltammetry of the three Ni–Lu complexes shows an overall ~410 mV shift in the Ni(0/I) redox couple, suggesting tunability of the Ni electronics across the series. Computational studies reveal polarized bonding interactions between the Ni 3d z 2 (major) and the Lu 5d z 2 (minor) orbitals, where the percentage of Lu character increases in the order: 4 (6.0% Lu 5d z 2 ) < 3-THF (8.5%) < 3 (9.3%). All three Ni–Lu complexes bind H 2 at low temperatures (-30 to -80 °C) and are competent catalysts for styrene hydrogenation. Complex 3 outperforms 4 with a four-fold faster rate. Additionally, adding increasing THF equivalents to 3, which would favor build-up of 3-THF, decreases the rate. We propose that altering the coordination sphere of the Lu support can influence the resulting properties and catalytic activity of the active Ni(0) metal center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Molecular chains of coordinated dimolybdenum isonicotinate paddlewheel clusters

A growing focus on the use of coordination polymers for active device applications motivates the search for candidate materials with integrated and optimized charge transport modes. We show herein the synthesis of a linear coordination polymer comprised of Mo 2 (INA) 4 (INA = isonicotinate) metal–organic clusters. Single-crystal X-ray structure determination shows that this cluster crystallizes into one-dimensional molecular chains, whose INA-linked Mo 2 cores engage in alternate axial and equatorial binding motifs along the chain axis. Electron paramagnetic resonance spectra, absorption spectra, and density functional theory calculations show that the aforementioned linear coordination environment significantly modifies the electronic structure of the clusters. This work expands the synthetic foundation for assembly of coordination polymers with tailorable dimensionalities and charge transport properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanistic investigation of the aerobic oxidation of 2-pyridylacetate coordinated to a Ru(ii) polypyridyl complex

A new ruthenium polypyridyl complex, [Ru(bpy) 2 (acpy)] + (acpy = 2-pyridylacetate, bpy = 2,2'-bipyridine), was synthesized and fully characterized. Distinct from the previously reported analog, [Ru(bpy) 2 (pic)] + (pic = 2-pyridylcarboxylate), the new complex is unstable under aerobic conditions and undergoes oxidation to yield the corresponding α-keto-2-pyridyl-acetate (acpyoxi) coordinated to the Ru II center. The reaction is one of the few examples of C–H activation at mild conditions using O 2 as the primary oxidant and can provide mechanistic insights with important implications for catalysis. Theoretical and experimental investigations of this aerobic oxidative transformation indicate that it takes place in two steps, first producing the α-hydroxo-2-pyridyl-acetate analog and then the final product. The observed rate constant for the first oxidation was in the order of 10 -2 h -1 . The reaction is hindered in the presence of coordinating solvents indicating the role of the metal center in the process. Theoretical calculations at the M06-L level of theory were performed for multiple reaction pathways in order to gain insights into the most probable mechanism. Our results= indicate that O 2 binding to [Ru(bpy) 2 (acpy)] + is favored by the relative instability of the six-ring chelate formed by the acpy ligand and the resulting Ru III -OO˙- superoxo is stabilized by the carboxylate group in the coordination sphere. C–H activation by this species involves high activation free energies (ΔG ‡ = 41.1 kcal mol -1 ), thus the formation of a diruthenium μ-peroxo intermediate, [(Ru III (bpy) 2 (O-acpy)) 2 O 2 ] 2+ via interaction of a second [Ru(bpy) 2 (acpy)] + was examined as an alternative pathway. The dimer yields two Ru IV =O centers with a low ΔG ‡ of 2.3 kcal mol -1 . The resulting Ru IV =O species can activate C–H bonds in acpy (ΔG ‡ = 23.1 kcal mol -1 ) to produce the coordinated α-hydroxo-2-pyridylacetate. Further oxidation of this intermediate leads to the α-keto-2-pyridyl-acetate product. The findings provide new insights into the mechanism of C–H activation catalyzed by transition-metal complexes using O 2 as the sole oxygen source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗