Facile Access to Cationic Methylstannylenes and Silylenes Stabilized by E-Pt Bonding and their Methyl Group Transfer Reactivity.

We describe a family of cationic methylstannylene and chloro- and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn:+ are stabilized by coordination to PtII and are formed by facile Me group transfer from dimethyl or monomethyl PtII complexes, in the latter case triggered by concomitant B-H, Si-H, and H2 bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl- removal from HSiCl3 under ambient conditions. The computational studies show that stabilization of cationic methylstannylenes and cationic silylenes is achieved through weak coordination to a neutral N-donor ligand binding pocket. The analysis of the electronic potentials, as well as the Laplacian of electron density, also reveals the differences in the character of Pt-Si vs. Pt-Sn bonding. We demonstrate the importance of a ligand-supported binuclear Pt/tetrel core and weak coordination to facilitate access to tetrylium-ylidene Pt complexes, and a transmetalation approach to the synthesis of MeSnII :+ derivatives.

Carbon Dioxide Electroreduction and Formic Acid Oxidation by Formal Nickel(I) Complexes of Di-isopropylphenyl Bis-iminoacenaphthene.

Processing CO2 into value-added chemicals and fuels stands as one of the most crucial tasks in addressing the global challenge of the greenhouse effect. In this study, we focused on the complex (dpp-bian)NiBr2 (where dpp-bian is di-isopropylphenyl bis-iminoacenaphthene) as a precatalyst for the electrochemical reduction of CO2 into CH4 as the sole product. Cyclic voltammetry results indicate that the realization of a catalytically effective pattern requires the three-electron reduction of (dpp-bian)NiBr2. The chemically reduced complexes [K(THF)6]+[(dpp-bian)Ni(COD)]- and [K(THF)6]+[(dpp-bian)2Ni]- were synthesized and structurally characterized. Analyzing the data from the electron paramagnetic resonance study of the complexes in solutions, along with quantum-chemical calculations, reveals that the spin density is predominantly localized at their metal centers. The superposition of trajectory maps of the electron density gradient vector field ∇ ρ r ${\nabla \rho \left({\bf r}\right)}$ and the electrostatic force density field F e s r ${{{\bf F}}_{{\rm e}{\rm s}}\left({\bf r}\right)}$ per electron, as well as the atomic charges, discloses that, within the first coordination sphere, the interatomic charge transfer occurs from the metal atom to the ligand atoms and that the complex anions can thus be formally described by the general formulae (dpp-bian)2-Ni+(COD) and (dpp-bian)2 -Ni+. It was also shown that the reduced nickel complexes can be oxidized by formic acid; resulting from this reaction, the two-electron and two-proton addition product dpp-bian-2H is formed.

Structural flexibility of favipiravir and its structural analogues in solutions: experimental and computational insight.

Combined UV-vis and quantum chemical studies of the structural flexibility and tautomerism of 6-R-3-hydroxy-2-pyrazine carboxamides in solutions revealed that their keto-enol transformations are accompanied by the deprotonation of enol tautomers and the formation of the corresponding anionic species. Both the solvent and the 6-R substituent strongly influence the relative abundance of the above forms in solutions. Anions are not formed in 1,2-dichloroethane (DCE), but the probability of deprotonation in neutral water and N,N-dimethylformamide (DMF) increases in the order R = H < F < NO2. Only enol tautomers of all solutes are found in DCE. DMF stabilizes keto forms only moderately and assists much strongly in the deprotonation of all three compounds. Water tends to stabilize both keto tautomers and deprotonated anions: the keto form dominates in the case of R = H (antiviral drug T-1105), the anions are found exclusively for R = NO2, and the aqueous solution of another antiviral drug, favipiravir (R = F), contains both the keto tautomer and the anionic form. The results of quantum chemical free energy calculations are in agreement with the experimental observations.

Adamantyl-ureas with pyrazoles substituted by fluoroalkanes as soluble epoxide hydrolase inhibitors.

A series of soluble epoxide hydrolase (sEH) inhibitors containing halogenated pyrazoles was developed. Inhibition potency of the obtained compounds ranges from 0.8 to 27.5 nM. 1-Adamantyl-3-[(4,5-dichloro-1-methyl-1Н-pyrazol-3-yl)methyl]urea (3f, IC50 = 0.8 nM) and 1-[(Adamantan-1-yl)methyl]-3-[(4,5-dichloro-1-methyl-1Н-pyrazol-3-yl)methyl]urea (4f, IC50 = 1.2 nM) were found to be the most potent sEH inhibitors within the described series.

Chemical and Electrochemical Reductions of Monoiminoacenaphthenes.

Redox properties of monoiminoacenaphthenes (MIANs) were studied using various electrochemical techniques. The potential values obtained were used for calculating the electrochemical gap value and corresponding frontier orbital difference energy. The first-peak-potential reduction of the MIANs was performed. As a result of controlled potential electrolysis, two-electron one-proton addition products were obtained. Additionally, the MIANs were exposed to one-electron chemical reduction by sodium and NaBH4. Structures of three new sodium complexes, three products of electrochemical reduction, and one product of the reduction by NaBH4 were studied using single-crystal X-ray diffraction. The MIANs reduced electrochemically by NaBH4 represent salts, in which the protonated MIAN skeleton acts as an anion and Bu4N+ or Na+ as a cation. In the case of sodium complexes, the anion radicals of MIANs are coordinated with sodium cations into tetranuclear complexes. The photophysical and electrochemical properties of all reduced MIAN products, as well as neutral forms, were studied both experimentally and quantum-chemically.

Synthesis, Structure, and Electrochemical Properties of 2,3,4,5-Tetraphenyl-1-Monophosphaferrocene Derivatives.

Heteroleptic 2,3,4,5-tetraphenyl-1-monophosphaferrocene [FeCp(η5-PC4Ph4)] was obtained at a 62% yield through the reaction of lithium 2,3,4,5-tetraphenyl-1-monophosphacyclopentadienide Li(PC4Ph4) (1) with [FeCp(η6-C6H5CH3)][PF6]. The structure of 1-monophosphaferrocene 2 and its W(CO)5-complex 3 were confirmed by multinuclear NMR and single-crystal X-ray diffraction study and further supported by DFT calculations. Cyclic voltammetry demonstrated that [FeCp(η5-PC4Ph4)] 2 has a quasi-reversible oxidation wave. The comparison of the properties of phosphaferrocene 2 with those of W(CO)5-complex 3 shows the possibility of changing the coordination type during oxidation.

Green Emissive Copper(I) Coordination Polymer Supported by the Diethylpyridylphosphine Ligand as a Luminescent Sensor for Overheating Processes.

Tertiary diethylpyridylphosphine was synthesized by the reaction of pyridylphosphine with bromoethane in a suberbasic medium. The reaction of phosphine with the copper(I) iodide led to the formation of a copper(I) coordination polymer, which, according to the X-ray diffraction data, has an intermediate structure with a copper-halide core between the octahedral and stairstep geometries of the Cu4I4 clusters. The obtained coordination polymer exhibits a green emission in the solid state, which is caused by the 3(M+X)LCT transitions. The heating up of the copper(I) coordination polymer to 138.5 °C results in its monomerization and the formation of a new solid-state phase. The new phase exhibits a red emission, with the emission band maximum at 725 nm. According to the experimental data and quantum chemical computations, it was concluded that depolymerization probably leads to a complex that is formed with the octahedral structure of the copper-halide core. The resulting solid-state phase can be backward-converted to the polymer phase via recrystallization from the acetone or DMF. Therefore, the obtained coordination polymer can be considered a sensor or detector for the overheating of processes that should be maintained at temperatures below 138 °C (e.g., engines, boiling liquids, solar heat systems, etc.).

Bulky PNP Ligands Blocking Metal-Ligand Cooperation Allow for Isolation of Ru(0), and Lead to Catalytically Active Ru Complexes in Acceptorless Alcohol Dehydrogenation.

We synthesized two 4Me-PNP ligands which block metal-ligand cooperation (MLC) with the Ru center and compared their Ru complex chemistry to their two traditional analogues used in acceptorless alcohol dehydrogenation catalysis. The corresponding 4Me-PNP complexes, which do not undergo dearomatization upon addition of base, allowed us to obtain rare, albeit unstable, 16 electron mono-CO Ru(0) complexes. Reactivity with CO and H2 allows for stabilization and extensive characterization of bis-CO Ru(0) 18 electron and Ru(II) cis and trans dihydride species that were also shown to be capable of C(sp2 ) -H activation. Reactivity and catalysis are contrasted to non-methylated Ru(II) species, showing that an MLC pathway is not necessary, with dramatic differences in outcomes during catalysis between i Pr and t Bu PNP complexes within each of the 4Me and non-methylated backbone PNP series being observed. Unusual intermediates are characterized in one of the new and one of the traditional complexes, and a common catalysis deactivation pathway was identified.

Real-Space Interpretation of Interatomic Charge Transfer and Electron Exchange Effects by Combining Static and Kinetic Potentials and Associated Vector Fields.

Intricate behaviour of one-electron potentials from the Euler equation for electron density and corresponding gradient force fields in crystals was studied. Channels of locally enhanced kinetic potential and corresponding saddle Lagrange points were found between chemically bonded atoms. Superposition of electrostatic ϕ e s r and kinetic ϕ k r potentials and electron density ρ r allowed partitioning any molecules and crystals into atomic ρ - and potential-based ϕ -basins; ϕ k -basins explicitly account for the electron exchange effect, which is missed for ϕ e s -ones. Phenomena of interatomic charge transfer and related electron exchange were explained in terms of space gaps between zero-flux surfaces of ρ - and ϕ -basins. The gap between ϕ e s - and ρ -basins represents the charge transfer, while the gap between ϕ k - and ρ -basins is a real-space manifestation of sharing the transferred electrons caused by the static exchange and kinetic effects as a response against the electron transfer. The regularity describing relative positions of ρ -, ϕ e s -, and ϕ k - basin boundaries between interacting atoms was proposed. The position of ϕ k -boundary between ϕ e s - and ρ -ones within an electron occupier atom determines the extent of transferred electron sharing. The stronger an H⋅⋅⋅O hydrogen bond is, the deeper hydrogen atom's ϕ k -basin penetrates oxygen atom's ρ -basin, while for covalent bonds a ϕ k -boundary closely approaches a ϕ e s -one indicating almost complete sharing of the transferred electrons. In the case of ionic bonds, the same region corresponds to electron pairing within the ρ -basin of an electron occupier atom.

H2 , B-H, and Si-H Bond Activation and Facile Protonolysis Driven by Pt-Base Metal Cooperation.

We report a series of heterobimetallic Pt/Zn and Pt/Ca complexes to study the effect of proximity of a dicationic base metal on the organometallic Pt species. Varying degrees of Pt⋅⋅⋅Zn and Zn interaction with the bridging Me group are achieved, showcasing snapshots of a hypothetical process of retrotransmetalation from Pt to Zn. In contrast, only weak interactions were observed for Ca with a Pt-bound Me group. Activation of H2 , B-H and Si-H bonds leads to the formation of hydride-bridged Pt-H-Zn complexes, which is not observed in the absence of Zn, pointing out the importance of metal-metal cooperation. Reactivity of PtMe2 /M2+ with terminal acetylene, water and methanol is also studied, leading to facile protonation of one of the Me groups at the Pt center only when Zn is present. This study sheds light on various ways in which the presence of a 2+ metal cation significantly affects the reactivity of a common organoplatinum complex.

Multicomponent Self-Assembly of Diaminobenzoquinonato-Bridged Manganese(I) Metallosupramolecular Rectangles: Host-Guest Interactions, Anticancer Activity, and Visible-Light-Induced CO Releasing Studies.

The one-pot self-assembly of Mn2(CO)10, a bis-chelated diaminobenzoquinonato (ON∩ON) bridge (L), and a linear ditopic linker (N∩N) (L') has resulted into the formation of M4L2L2'-type manganese(I)-based tetranuclear metallorectangles of the general formula [{(CO)3Mn(µ-η4-L)Mn(CO)3}2(µ-(N-N)2)] (1-8), wherein L is 2,5-bis(n-butylamine)-1,4-benzoquinone (bbbq) and/or 2,5-bis(phenethylamino)-1,4-benzoquinone (bpbq) and N-N is 4,4'-bipyridine (bpy), trans-1,2-bis(4-pyridyl) ethylene (bpe), phenyl-1,4-bis(isonicotinate) (pbin), and N,N'-bis(4-pyridylformamide)-1,4-benzene (bpfb). Metallorectangles 1-8 were characterized by infrared, ultraviolet-visible (UV-vis) absorption, and 1H nuclear magnetic resonance spectroscopies, elemental analysis, and electrospray ionization-mass spectrometry. The molecular and crystal structures of 1•n(CHCl3) and coronene⊂3•coronene were determined by the single-crystal X-ray diffraction method. Host-guest binding abilities of 1, 3, and 7 with coronene, pyrene, and 4,4'-dihydroxybiphenyl were investigated using UV-vis absorption and emission spectroscopic techniques. Formation of host-guest complexes was further confirmed by the single-crystal X-ray structural analysis. Absorption of spectra of these metallorectangles showed high-intensity metal-ligand charge transfer as a broad band in the visible region. In vitro cytotoxicity assays were performed on 1, 3, 5, and 7 against lung, colon, and cervical cancer cells as well as normal cells. Compounds 5 and 7 were identified as visible-light-induced CO-releasing molecules from the myoglobin assay.

Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes.

A novel representative of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide containing a chloro substituent in the meta-position of the aryl groups was obtained with a high yield based on the reaction of tributyl(1,2,3-triarylcyclopropenyl)phosphonium bromide and sodium polyphosphides. Further reaction of sodium 3,4,5-tris(3-chlorophenyl)-1,2-diphosphacyclopentadienide with [FeCp(η6-C6H5CH3)][PF6] complex gives a new 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene. The electrochemical properties of 3,4,5-tris(3-chlorophenyl)-1,2-diphosphaferrocene were studied and compared to 3,4,5-tris(4-chlorophenyl)-1,2-diphosphaferrocene. It was found that the position of the chlorine atom on the aryl fragment has an influence on the reduction potential of 1,2-diphosphaferrocenes, while the oxidation potentials do not change.

Orbital-Free Quantum Crystallographic View on Noncovalent Bonding: Insights into Hydrogen Bonds, π⋠⋠⋠π and Reverse Electron Lone Pair⋠⋠⋠π Interactions.

A detailed analysis of a complete set of the local potentials that appear in the Euler equation for electron density is carried out for noncovalent interactions in the crystal of a uracil derivative using experimental X-ray charge density. The interplay between the quantum theory of atoms in molecules and crystals and the local potentials and corresponding inner-crystal electronic forces of electrostatic and kinetic origin is explored. Partitioning of crystal space into atomic basins and atomic-like potential basins led us to the definite description of interatomic interaction and charge transfer. Novel physically grounded bonding descriptors derived within the orbital-free quantum crystallography provided the detailed examination of π-stacking and intricate C=O⋅⋅⋅π interactions and nonclassical hydrogen bonds present in the crystal. The donor-acceptor character of these interactions is revealed by analysis of Pauli and von Weizsäcker potentials together with well-known functions, e. g., deformation electron density and electron localization function. In this way, our analysis throws light on aspects of these closed-shell interactions hitherto hidden from the description.

Assembly of Heterometallic AuICu2I2 Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine.

The row of metallocyclic dinuclear gold(I) complexes with cyclic diphosphines, namely, P-pyridylethyl-substituted 1,5-diaza-3,7-diphosphacyclooctanes, has been obtained. Further interaction of the dinuclear gold(I) complexes with copper(I) iodide gave the first examples of hexanuclear AuI/CuI complexes containing two unusual trinuclear AuICu2I2 fragments. The structures of di- and hexanuclear complexes were confirmed by NMR spectroscopy, ESI mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. All of the obtained complexes are moderate emitters in the solid state. Dinuclear gold(I) complexes displayed a greenish emission with the maxima in the emission spectra at ca. 550 nm. The obtained hexanuclear heterobimetallic AuI/CuI complexes are triplet solid-state blue emitters with the maximum in the emission spectra at 463 and 484 nm. According to the TD-DFT calculations, the observed emission of all studied complexes had a triplet origin and was caused by the 3CC or 3(MLCT) T1 → S0 transitions for dinuclear and hexanuclear complexes, respectively.

Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High-Valent Nickel Complexes.

We describe a series of air-stable NiIII complexes supported by a simple, robust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled by the CF3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of NiII to NiIII . These NiIII complexes act as efficient catalysts for photoinduced C(sp2 )-H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light-mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late-stage functionalization of drug analogs.

Dynamic PdII /CuI Multimetallic Assemblies as Molecular Models to Study Metal-Metal Cooperation in Sonogashira Coupling.

Cooperation between two different metals plays a crucial role in many synergistic catalytic reactions, such as the Sonogashira C-C cross-coupling reaction, where an interaction between the Pd and Cu centers is proposed in the transmetalation step. Although several heterobimetallic Pd/Cu complexes were proposed as structural models of the active species in Sonogashira coupling, the detailed understanding of the metal-metal cooperation in transmetalation is still lacking in current systems. In this work, we report a stepwise and systematic approach to building heteromultimetallic Pd/Cu assemblies as a tool to study metal-metal cooperativity. We obtained fully characterized Pd/Cu multimetallic assemblies that show reactivity in alkyne activation, formation of catalytically relevant aryl/acetylide species, and C-C elimination, serving as functional models for Sonogashira reaction intermediates. The combined experimental and DFT studies highlight the importance of ligand-controlled coordination geometry, metal-metal distances and dynamics of the multimetallic assembly for transmetalation step.

The Assembly of Unique Hexanuclear Copper(I) Complexes with Effective White Luminescence.

The unique L2Cu6I6 complexes containing two Cu3I3 units have been obtained via reaction of 1,5-diaza-3,7-diphosphacyclooctanes bearing ethylpyridyl substituents at phosphorus atoms with an excess of copper iodide. The structure of one of the complexes was confirmed by X-ray diffraction. It was shown that the complexes can exist in two crystalline phases with different parameters of the unit cell, which were detected by the PXRD data analyses. The solvent-free crystalline phases of the complexes display rare solid-state white emission at room temperature, which is observed due to the presence of two broad bands in the emission spectra with maxima at 464 and 610 nm. Quantum chemical computations show that the high-energy band has 3(M+X)LCT origin, whereas the low-energy band is interpreted as 3CC. The quantum yields of white luminescence of complexes reach 15-20%.

Intriguing Near-Infrared Solid-State Luminescence of Binuclear Silver(I) Complexes Based on Pyridylphospholane Scaffolds.

A series of novel charged disilver(I) complexes with pyridyl-containing phospholanes was synthesized. These complexes were characterized using a range of spectroscopic techniques and single-crystal and powder X-ray diffraction. The complexes demonstrate solid-state near-infrared (NIR) luminescence (765-902 nm) that is unique for dinuclear AgI complexes. Combined spectroscopic/quantum chemical analysis suggests that the NIR luminescence of complexes 4-6 in the solid state is mainly due to crystal packing effects.

Adamantyl thioureas as soluble epoxide hydrolase inhibitors.

A series of inhibitors of the soluble epoxide hydrolase (sEH) containing one or two thiourea groups has been developed. Inhibition potency of the described compounds ranges from 50 µM to 7.2 nM. 1,7-(Heptamethylene)bis[(adamant-1-yl)thiourea] (6f) was found to be the most potent sEH inhibitor, among the thioureas tested. The inhibitory activity of the thioureas against the human sEH is closer to the value of activity against rat sEH rather than murine sEH. While being less active, thioureas are up to 7-fold more soluble than ureas, which makes them more bioavailable and thus promising as sEH inhibitors.

Interplay between the Conformational Flexibility and Photoluminescent Properties of Mononuclear Pyridinophanecopper(I) Complexes.

The macrocyclic ligand conformational behavior in solution, solid-state structures and the photophysical properties of copper(I) cationic and neutral mononuclear complexes supported by tetradentate N, N'-dialkyl-2,11-diaza[3.3](2,6)-pyridinophane ligands RN4 (R = H, Me, iBu, secBu, neoPent, iPr, Ts) were investigated in detail. Steric properties of the alkyl group at the axial amine in the RN4 ligand were found to strongly affect the conformational preferences and dynamic behavior in solution. Several types of conformational exchange processes were revealed by variable-temperature NMR and 2D exchange spectroscopy, including degenerative exchange in a pseudotetrahedral species as well as exchange between two isomers with different conformers of tri- and tetracoordinate RN4 ligands. These exchange processes are slower for the complexes containing bulky alkyl groups at the amine compared to less sterically demanding analogues. A clear correlation is also observed between the steric bulk of the alkyl substituents and the photoluminescent properties of the derived complexes, with less dynamic complexes bearing bulkier alkyl substituents exhibiting higher absolute photoluminescence quantum yield (PLQY) in solution and the solid state: PLQY in solution increases in the order Me < neoPent < iBu < secBu ≈ iPr < tBu. The electrochemical properties of the cationic complexes [(RN4)CuI(MeCN)]X (X = BF4, PF6) were also dependent on the steric properties of the amine substituent.