A series of ruthenium(II) organometallic complexes incorporating pyridine-2-carboxylato ligand: Detailed spectroscopic and computional studies

The reaction of Ru(κ2C,O-RL)(PPh3)2(CO)Cl, 1 with excess sodium salt of pyridine-2-carboxylic acid (Napic) furnishes the complexes of the type Ru(κ1C-RL)(PPh3)2(CO) (pic), 2(R) with excellent yield (κ2C,O-RL is C6H2O-2-CHNHC6H4R(p)-3-Me-5, κ1C-RL is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is Me, OMe, Cl). The chelation of pic is attended with the cleavage of Ru–O and Ru–Cl bonds and iminium–phenolato→imine–phenol prototropic shift. The 1 ​→ ​2 conversion is irreversible and the type 2 species are thermodynamically more stable than the acetate, nitrite and nitrate complexes of 1. The spectral (UV–vis, IR, 1H NMR) and electrochemical data of the complexes are reported. In dichloromethane solution the complexes display one quasi–reversible RuIII/RuII cyclic voltammetric response with E1/2 in the range 0.72–0.80 ​V vs. Ag/AgCl. The crystal and molecular structure of Ru(κ1C-MeOL)(PPh3)2(CO)(pic)∙CH3CN is reported which revealed distorted octahedral RuC2P2NO coordination sphere. The pairs (P, P), (C, O) and (C, N) define the three trans directions. The electronic structures of the complexes are also scrutinized by density functional theory (DFT) and time–dependent density functional theory (TD–DFT) calculations.     

Synthesis,spectroscopic, DFT,biological studies and molecular docking of oxovanadium (IV), copper (II) and iron (III) complexes of a new hydrazone derived from heterocyclic hydrazide

A new Schiff base hydrazone (Z)‐2‐(2‐aminothiazol‐4‐yl)‐N′‐(2‐hydroxy‐3‐methoxybenzylidene) acetohydrazide (H₂L) and its chelates [VO (HL)₂]·5H₂O, [Cu (HL)Cl(H₂O)]·2H₂O and [Fe(L)Cl(H₂O)₂]·3H₂O have been isolated and characterized using different physico‐chemical methods, for example infrared (IR), electron paramagnetic resonance (EPR), thermogravimetric analysis and DTG in the solid state, and ¹H‐NMR, ¹³C‐NMR and UV in solution. Magnetic and UV–visible measurements proposed that the coordination environments are square pyramidal, tetrahedral and octahedral geometries for oxovanadium (IV), Cu (II) and Fe (III), respectively. The ligand acts as mono‐negative NO towards oxovanadium (IV) and Cu (II) ions, and bi‐negative ONO for Fe (III) ion. The geometries of the ligand and its complexes were performed using Gaussian 9 program with density functional theory. The EPR spectral data of oxovanadium (IV) and Cu (II) chelates confirmed the mentioned geometries. The molecular modeling was done, and illustrated bond lengths, bond angles, molecular electrostatic potential, Mulliken atomic charges and chemical reactivity for the inspected compounds. Theoretical IR and ¹H‐NMR of the free ligand were calculated. Furthermore, thermodynamic and kinetic parameters for thermal decomposition steps were studied. Docking study of H₂L was applied against the proteins of both bacterial strains Staphylococcus aureus and Escherichia coli, as well as the protein of xanthine oxidase as antioxidant agent by Schrödinger suite program utilizing XP glide protocol. Furthermore, antimicrobial, antioxidant and DNA‐binding activities of the compounds have been carried out.     

Synthesis,characterization and antibacterial studies of Tm(III), Yb(III) and Lu(III) complexes of morin

New solid amorphous compounds of Tm(III), Yb(III) and Lu(III) with morin have been synthesized. Their composition and some physicochemical properties have been studied by elemental analysis, thermogravimetric analysis, IR spectroscopy as well as by conductivity, UV/Vis, MS, and NMR spectroscopies in solution. The spectroscopic studies have indicated that the 3-OH hydroxyl group and the carbonyl oxygen of morin were involved in the coordination of metal ion. The antibacterial activity of the synthesized compounds has been determined by the cylinder-plate diffusion and dilution methods (determination of minimum inhibitory concentration).     

Density functional study on zerovalent lanthanide bis(arene)-sandwich complexes

Several zerovalent lanthanide bis(arene)-sandwich complexes, Ln(η⁶-C₆H₆)₂, Ln = La, Ce, Eu, Gd and Lu, have been studied by means of density functional theory. The calculated geometries are in good agreement with experiment. The calculated dissociation energies of the bond Ln-(η⁶-C₆H₆) may be considerably underestimated, but they correctly reveal the variation regularity. The bonding in these molecules can be described in terms of a relatively weak π-electron donation from benzene to Ln and a stronger electron back-donation from Ln 5d to the benzene π* orbitals. During bond formation, there is electron promotion from Ln 6s to 5d instead of from 4f to 5d, in opposition to the proposal of Anderson et al. The relativistic effect only slightly influences the molecular geometry, but decreases the bonding energy considerably through lowering the Ln 6s level and raising the 5d level. It enhances the trend of the bonding energy to decrease along the lanthanide series. Received: 22 June 1998 / Accepted: 9 September 1998 / Published online: 17 December 1998     

Investigation on the isoform selectivity of novel kinesin-like protein 1 (KIF11) inhibitor using chemical feature based pharmacophore,molecular docking,and quantum mechanical studies

Kinesin-like protein (KIF11) is a molecular motor protein that is essential in mitosis. Removal of KIF11 prevents centrosome migration and causes cell arrest in mitosis. KIF11 defects are linked to the disease of microcephaly, lymph edema or mental retardation. The human KIF11 protein has been actively studied for its role in mitosis and its potential as a therapeutic target for cancer treatment. Pharmacophore modeling, molecular docking and density functional theory approaches was employed to reveal the structural, chemical and electronic features essential for the development of small molecule inhibitor for KIF11. Hence we have developed chemical feature based pharmacophore models using Discovery Studio v 2.5 (DS). The best hypothesis (Hypo1) consisting of four chemical features (two hydrogen bond acceptor, one hydrophobic and one ring aromatic) has exhibited high correlation co-efficient of 0.9521, cost difference of 70.63 and low RMS value of 0.9475. This Hypo1 is cross validated by Cat Scramble method; test set and decoy set to prove its robustness, statistical significance and predictability respectively. The well validated Hypo1 was used as 3Dquery to perform virtual screening. The hits obtained from the virtual screening were subjected to various scrupulous drug-like filters such as Lipinski’s rule of five and ADMET properties. Finally, six hit compounds were identified based on the molecular interaction and its electronic properties. Our final lead compound could serve as a powerful tool for the discovery of potent inhibitor as KIF11 agonists.     

Crystal structures,theoretical calculations,spectroscopic and electrochemical properties of Cr(III) complexes with dipicolinic acid and 1,10-phenantroline

The crystal structures of compounds Na[Cr(dipic)₂] · 2H₂O (1) and [Cr(dipic)(phen)Cl] · 1/2H₂O (2), dipic = dipicolinate, phen = 1,10-phenantroline, were determined. In both complexes, Cr(III) is in a distorted octahedral environment. In complex (1), the metal is coordinated to two nearly perpendicular dipic anions acting as tridentate ligands through one oxygen of each carboxylate group and the pyridinic nitrogen atom. In complex (2), Cr(III) ion is similarly coordinated to a dipic anion, defining a ligand equatorial plane. The phen molecule bridges the remaining equatorial coordination site and one of the axial positions through its N-atoms. The other axial position is occupied by a chloride ion.     

Thermal and spectroscopic studies of sodium and light lanthanide (III) complexes with 2,4-pyridinedicarboxylate anion

Pyridine-2,4-dicarboxylic acid (lutidinic acid) is next one after pyridine-2,5-dicarboxylic acid of the six isomers which lanthanide complexes were studied thermally and spectrally. New complexes synthesized with light lanthanides (III) with general formula Ln₂L₃·nH₂O, where n?=?7.5; 8; 8.5; 9, were obtained. Sodium salt was obtained as hexahydrated compound. Hydrated complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), and Gd(III) are thermally stable up to 303?C313?K. Dehydration process run for all compounds in one stage, anhydrous compounds decompose through appropriate light lanthanides (III) oxalates, oxocarbonates, carbonates to metal oxides. Theoretical IR and Raman studies were carried out in order to identify precisely characteristic group bands vibrations present on IR and Raman spectra.     

Some contribution to W(VI)-peroxo-chemistry: Synthesis,spectroscopic characterization,reactivity and DFT studies

Synthesis of white microcrystalline oxodiperoxotungstate(VI) complexes, K[WO(O₂)₂(L)(H₂O)]·H₂O, (L ?= ?salicylate, 5-chlorosalicylate, 4-hydroxybenzoate) have been achieved from reaction of Na₂WO₄·2H₂O with 30% H₂O₂ and the respective hetero-ligands at pH Ca. 7–7.5 in aqueous medium. The newly synthesized compounds were comprehensively characterized by elemental analyses, spectral studies, room temperature magnetic moment measurements and mass spectrometric studies. Infrared spectra suggest that, peroxo groups are bonded to the WO⁺⁴ center in a triangular bidentate (C_2v) fashion and the hetero-ligands benzene-core hydroxycarboxylic acids viz. salicylic acid, 5-chlorosalicylic acid, 4-hydroxybenzoic acid in anoinic form are coordinated in monodentate manner. Compounds are fairly stable in aqueous solution for sufficient period of time. The results of mass spectrometric analysis lend support to the molecular composition of the complexes ascertained on the basis of elemental analyses and spectroscopic studies. Compound potassium(aquo)(5-chlorosalicylato)oxodiperoxotungstate(VI)monohydrate, K[WO(O₂)₂(5-chlorosalicylate)(H₂O)]·H₂O, act as an oxidant of bromide ion in aqueous phase bromination of chosen organic substrates to their corresponding bromo organics. Density Functional Theory (TD-DFT) calculations were performed on the synthesized complexes substantiated the experimentally obtained results. The TD-DFT optimized structures are in excellent agreement with the results of elemental analyses, spectral as well as mass spectrometric data.     

Paramagnetic ruthenium(III) cyclometallated complex. Synthesis, spectroscopic studies and electron-transfer properties

The reaction of Ru^II(PPh₃)₃X₂ (X = Cl, Br) with o-(OH)C₆H₄C(H)=N-CH₂C₆H₅ (HL) under aerobic conditions affords Ru^II(L)₂(PPh₃)₂, 1, in which both the ligands (L) are bound to the metal center at the phenolic oxygen (deprotonated) and azomethine nitrogen and Ru^III(L¹)(L²)(PPh₃), 2, in which one L is in bidentate N,O form like in complex 1 and the other ligand is in tridentate C,N,O mode where cyclometallation takes place from the ortho carbon atom (deprotonated) of the benzyl amine fragment. The complex 1 is unstable in solution, and undergoes spontaneous oxidative internal transformation to complex 2. In solid state upon heating, 1 initially converts to 2 quantitatively and further heating causes the rearrangement of complex 2 to the stable RuL₃ complex. The presence of symmetry in the diamagnetic, electrically neutral complex 1 is confirmed by ¹H and ³¹P NMR spectroscopy. It exhibits an Ru^II → L, MLCT transition at 460 nm and a ligand based transition at 340 nm. The complex 1 undergoes quasi-reversible ruthenium(II)—ruthenium(III) oxidation at 1.27V vs. SCE. The one-electron paramagnetic cyclometallated ruthenium(III) complex 2 displays an L → Ru^III, LMCT transition at 658 nm. The ligand based transition is observed to take place at 343 nm. The complex 2 shows reversible ruthenium(III)—ruthenium(IV) oxidation at 0.875V and irreversible ruthenium(III)—ruthenium(II) reduction at −0.68V vs. SCE. It exhibits a rhombic EPR spectrum, that has been analysed to furnish values of axial (6560 cm⁻¹) and rhombic (5630 cm⁻¹) distortion parameters as well as the energies of the two expected ligand field transitions (3877 cm⁻¹ and 9540 cm⁻¹) within the t₂ shell. One of the transitions has been experimentally observed in the predicted region (9090 cm⁻¹). The first order rate constants at different temperatures and the activation parameter ΔH^#/ΔS^# values of the conversion process of 1 → 2 have been determined spectrophotometrically in chloroform solution.     

Density functional study of lanthanide complexes (η-C5H5)2LnX·OC4H8 (Ln=La-Lu; X=F, Cl, Br and I)

Density functional calculations were performed on a series of mixed-ligand organolanthanide complexes, (η⁵-C₅H₅)₂LnX·OC₄H₈ (η⁵-C₅H₅=Cp; Ln=La-Lu; X=F, Cl, Br and I; OC₄H₈=THF). The calculated geometrical parameters are in reasonable agreement with the experimental data. The distances between Ln and ligands follow linearity along the ionic radius of lanthanide metal, as the same as that observed in experiment. In the mixed-ligand complexes, Ln-Cp and Ln-THF bonds are more covalent compared to Ln-X. The lanthanide contraction of various bond and the metal-ligand interaction energy followed the order of Ln-X>Ln-Cp>Ln-OC₄H₈. The orbital population and dipole moment were also discussed.     

Cobalt(II) complexes of biologically active glutathione: spectroscopic and molecular modeling studies

Cobalt(II) complexes of reduced glutathione (GSH) of general composition Na[Co(L)(X)].nH2O (where H2L = GSH; X = Cl-, NO3-, NCS-, CH3CO2-, HCO2-, ClO4- and n = 0-4) have been synthesized and characterised by elemental analyses, vibrational spectra, electronic spectra, magnetic susceptibility measurements, thermal studies and molecular modeling studies. Electronic spectra indicate planar geometry for all the complexes. Infrared spectra indicate the presence of H2O molecules (except perchlorate complex) in the complexes that has been supported by TG/DTA. The room temperature magnetic moment values for all complexes lie in the range of 2.60-2.80 BM range indicating departure from spin only values due to second order Zeeman effect. Thermal decomposition of all the complexes proceeds via first order kinetics. The Na[Co(L)(Cl)].2H2O complex has the minimum activation energy and Na[Co(L)(CH3CO2)].3H2O has the maximum activation energy. The molecular modeling calculation for energy minimization optimizes geometry of the metal complexes.     

Synthesis, spectroscopic and theoretical studies of two novel tripodal imine-phenol ligands and their complexation with Fe(III)

Two novel tripodal imine-phenol ligands, cis,cis-1,3,5-tris{(2-hydroxybenzilidene)aminomethyl}cyclohexane (TMACHSAL, L¹) and of cis,cis-1,3,5-tris{[(2-hydroxyphenyl)ethylidene]aminomethyl}cyclohexane (Me₃-TMACHSAL, L²) have been synthesized and characterized by elemental analyses and various spectral (UV–vis, IR and ¹H and ¹³C NMR) data. The complexation reactions of the ligands with H⁺ and Fe(III) were investigated by potentiometric and spectrophotometric methods at an ionic strength of 0.1 M KCl and 25 ± 1 °C in aqueous medium. Three protonation constants each for ligands L¹ and L² were determined and were used as input data to evaluate the formation constants of the metal complexes. Formations of metal complexes of the types FeLH₃, FeLH₂, FeLH, FeL and FeLH₋₁ were depicted in solution. Experimental evidences suggested for a formation of tris(iminophenolate) type metal complex by the ligands. The ligand L¹ showed higher affinity towards iron(III) than L². The pFe value related to L¹ (pFe = 20.14) is approximately four units higher than L² (pFe = 16.41) at pH = 7.4. The structures of the metal complexes were proposed through the molecular mechanics calculation using MM3 force field followed by semi-empirical PM3 method.     

Half-sandwich ruthenium(II)-arene complexes: synthesis,spectroscopic studies,biological properties,and molecular modeling

In search for antitumor metal-based drugs that would mitigate the severe side-effects of cisplatin, Ru(II) complexes are gaining increasing recent interest. In this work, we report on the synthesis, characterization (¹H- and ¹³C-NMR, FT-IR), and cytotoxicity studies of two new half-sandwich organometallic Ru(II) complexes of the general formula [Ru(η⁶-arene)(XY)Cl](PF₆) where arene?=?benzene or toluene and XY?=?bidentates: dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or 2-(9-anthryl)-1H-imidazo[4,5-f][1,10]phenanthroline (aip), which are bound to Ru(II) via two phenanthroline-N atoms in a characteristic “piano-stool” configuration of Ru(II)-arene complexes—as confirmed by vibrational and NMR spectra. In addition, cytotoxic studies were performed for similar half-sandwich organometallic [Ru(η⁶-p-cymene)(Me₂dppz)Cl]PF₆ complex (Me₂dppz = 11,12-dimethyl-dipyrido[3,2-a:2′,3′-c]phenazine). This study is complemented with elaborate modeling with density functional theory (DFT) calculations, which provided insight into reactive sites of Ru(II) structures, further detailed by molecular docking on the B-DNA dodecamer, which identified binding sites and affinities: most pronounced for the [Ru(η⁶-benzene)(aip)Cl](PF₆) in both A-T and G-C regions of the DNA minor groove. Cytotoxic activity was probed versus tumor cell lines B16, C6, and U251 (B16 mouse melanoma, C6 rat glioma, U251 human glioblastoma) and non-tumor cell line HACAT (HACAT normal human keratinocytes).     

An investigation of methods for the application of molecular mechanics to lanthanide complexes

Methods are described for molecular mechanics calculations on lanthanide complexes. The irregularity of the coordination spheres of these metals necessitate special treatment in a molecular mechanics force field. Three different methods for treating the metal coordination sphere in the complexes are evaluated. In the first method, we include bond stretch terms between metal and donor atoms and 1,3 interactions between donor atoms. The second method utilizes a nonbonded potential between metal atoms and donor atoms to determine the geometry of the coordination sphere, and the third method involves coulombic interactions as well as a nonbonded potential to describe the van der Waals interactions. Evaluations of the three methods have been carried out by calculating the r.m.s. deviations between experimental structures and minimized structures. Results indicate that it is possible to achieve good agreement by all three methods, but that the second method provides the most consistent results, as well as being relatively straightforward to paramaterize.     

Novel lithocholaphanes: Syntheses, NMR, MS, and molecular modeling studies

Novel head-to-head lithocholaphanes 6 and 11 have been synthesized via precursors 1–5 and 7–10 with overall good yields, and characterized by ¹H, ¹³C, and ¹⁵N NMR spectroscopy, ESI-TOF mass spectrometry, thermal analysis, and molecular modeling. In addition, the binding abilities of 6 and 11 towards alkali metal cations have been investigated via competitive complexation studies using equimolar mixtures of Li⁺, Na⁺, K⁺, and Rb⁺-cations, and cholaphanes 6 and 11. The formation of cation–cholaphane adducts was detected by ESI-TOF mass spectrometry. The trends in these comparative binding studies are nicely reproduced theoretically with PM3 energetically optimized structures of 6 and 11 and their interaction energies with alkali metal cations calculated by molecular mechanics. Cholaphane 11 possessing a peptoid type structural fragment, –(CH₂CONHCH₂CH₂)₂O–, as a coordination sphere, shows binding tendency towards lithium and sodium cations, whereas 6 possessing an ester type, –(CH₂OCOCH₂)₂O–, moiety and a bigger cavity size than 11, shows merely a tendency towards bigger alkali metal cations, potassium and rubidium.     

Vibrational spectra of mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes: Density functional theory calculations

The vibrational (IR and Raman) spectra of neutral and reduced mixed (phthalocyaninato)(porphyrinato) yttrium(III) double-decker complexes Y(Pc)(Por) and [Y(Pc)(Por)]⁻ [the simplified models of mixed (phthalocyaninato)(porphyrinato) rare earth(III) complexes] are studied using density functional theory (DFT) calculations. The simulated IR and Raman spectra of Y(Pc)(Por) are compared with the experimental IR spectrum of Tb(Pc)(TClPP) and Raman spectrum of Y(Pc)(TClPP), respectively, and many bands can acceptably fit in spite of the different species. On the basis of comparison with the simulated spectra of PbPc and PbPor together with the assistance of normal coordinate analysis, the calculated frequencies in their IR and Raman spectra are identified in terms of the vibrational mode of different ligand for the first time. The calculated frequency at 1048 cm⁻¹ in the IR spectrum of [Y(Pc)(Por)]⁻ with contribution from both Pc and Por vibrational modes is the characteristic IR vibrational mode of the reduced double-decker, while the characteristic IR vibrational mode of Y(Pc)(Por) attributed from the vibration of phthalocyanine monoanion radical Pc⁻ appears at 1257 cm⁻¹. In line with our previous experimental findings that the Raman spectra of M(Pc)(TPP) and M(Pc)(TClPP) are dominated by the Pc vibrational modes, theoretical calculations indicate that most of the Raman vibrational modes contributed from Por ring are covered up by those of Pc ring and thus are hard to be recognized in the Raman spectra of [Y(Pc)(Por)]⁻ and Y(Pc)(Por) due to their much weaker intensity in comparison with that of Pc ligand. Comparison in the IR and Raman spectra between [Y(Pc)(Por)]⁻ and Y(Pc)(Por) also suggests the localization of hole on the Pc ring in the neutral double-decker Y(Pc)(Por). The present work, representing the first detailed DFT study on the vibrational spectra of mixed (phthalocyaninato)(porphyrinato) rare earth(III) double-decker complexes, is useful in helping to understand the vibrational spectroscopic properties of this series of mixed tetrapyrrole ring complexes.     

Preparation, characterization, and the molecular structure of 2,4,6-trinitro-mesitylene

We reported in this study the synthesis, culture of crystal, and single-crystal X-ray crystallography of the 2,4,6-trinitro-trimethylbenzene (TNTM) compound. We found the crystal belongs to the Triclinic system with space group P-1. The compound was also characterized by FT-IR,¹H NMR, and MS spectroscopy techniques. Density functional theory (DFT) B3LYP was employed to optimize structure and calculate frequencies of TNTM. The calculated geometrical parameters are close to the corresponding experimental ones. The thermal decomposition of TNTM was investigated by DSC and TG–DTG methods at heating rate 10°C/min. The results indicate that TNTM has high heat-resistant ability.1

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Paramagnetic properties and molecular structure of coordination saturated inclusive lanthanide complexes with 18-crown-6 using NMR

Earlier NMR spectra of lanthanide complexes [Ln(18-crown-6)(NO₃)₃] have been analyzed by us (Babailov in Inorg Chem 51(3):1427–1433, 2012), where Ln³⁺ = La³⁺ (I), Ce³⁺ (II), Pr³⁺ (III) and Nd³⁺ (IV). The NMR signal assignment and conformational molecular dynamic have been found by 1D NOE and relaxation spectroscopy as well as on 2D NOESY and EXSY experiments at 170 K. In the present paper the ¹H NMR method is used to study the features of paramagnetic properties of complexes I–IV and [Eu(18-crown-6)(NO₃)₃] (V) at ambient temperature. The investigation was carried out by special method based on analysis of Δδ/z> on k(Ln)/z> (where k(Ln) is Bleaney’s constant, Δδ is paramagnetic contribution to the lanthanide-induced shifts). The obtained results indicate that the structure of the complexes (in CDCl₃ and CD₂Cl₂) are very similar.