Spectral,crystallographic, theoretical and antibacterial studies of palladium(II)/platinum(II) complexes with unsymmetric diphosphine ylides

The reaction of α‐keto‐stabilized diphosphine ylides [Ph₂P(CH₂)_nPPh₂═C(H)C(O)C₆H₄‐p‐CN] (n = 1 (Y¹); n = 2 (Y²)) with dibromo(1,5‐cyclooctadiene) palladium(II)/platinum(II) complexes, [Pd/PtBr₂(cod)], in equimolar ratio gave the new cyclometalated Pd(II) and Pt(II) complexes [Br₂Pd(κ²‐Y¹)] ( 1 ), [Br₂Pt(κ²‐Y¹)] ( 2 ), [Br₂Pd(κ²‐Y²)] ( 3 ) and [Br₂Pt(κ²‐Y²)] ( 4 ). These compounds were screened in a search for novel antibacterial agents and characterized successfully using Fourier transfer infrared and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. Also, the structures of complexes 1 and 2 were characterized using X‐ray crystallography. The results showed that the P,C‐chelated complexes 1 and 2 have structures consisting of five‐membered rings, while 3 and 4 have six‐membered rings, formed by coordination of the ligand through the phosphine group and the ylidic carbon atom to the metal centre. Also, a theoretical study of the structures of complexes 1 – 4 was conducted at the BP86/def2‐SVP level of theory. The nature of metal–ligand bonds in the complexes was investigated using energy decomposition analyses (EDA) and extended transition state combined with natural orbitals for chemical valence analyses. The results of EDA confirmed that the main portions of ΔE_int, about 57–58%, in the complexes are allocated to ΔE_elstat.     

Molecular structure and character of bonding of mono and divalent metal cations (Li+, Na+, K+, Mg2+, Ca2+, Zn2+, and Cu+) with guanosine: AIM and NBO analysis

The B3LYP/6-311++G (d,p) density functional approach was used to study the gas-phase metal affinities of Guanosine (ribonucleoside) for the Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺, and Cu⁺ cations. In this study we determine coordination geometries, binding strength, absolute metal ion affinities, and free energies for the most stable products. We have also compared the results for Guanosine, with our previously reported results for 2′-Deoxyguanosine. Based on the results, it is obvious that MIA is strongly dependent on the charge-to-size ratio of the cation. Guanosine interacts more strongly with Zn²⁺ than do with Mg²⁺, Ca²⁺, and Cu⁺ and therefore stronger interactions lead to higher MIA. In both free molecules and their complexes, the Syn orientation of the base is stabilized by an intramolecular O5′–H···N3 hydrogen bond and the anti orientation of the base is stabilized by an intramolecular C–H···O hydrogen bond formed between the (C8-H8) and the O5′ atom of the sugar moiety. It is also interesting to mention that linear correlation between calculated MIA values and the atomic numbers (Z) of the metal ions of Li⁺, Na⁺, and K⁺ were found. Furthermore, the influences of metal cationization on the strength of the N-glycosidic bond, torsion angles, angle of pseudorotation (P), and intramolecular C–H···O and O–H···O hydrogen bonds have been studied. Natural bond orbital (NBO) analysis was performed to calculate the charge transfer and natural population analysis of the complexes. Quantum theory of atoms in molecules (QTAIM) was also applied to determine the nature of interactions.     

SOLVENT-FREE CONVERSION OF OXIRANES TO THIIRANES WITH THIOUREA

A simple and efficient method for the conversion of various oxiranes to the corresponding thiiranes using thiourea under solvent free conditions is described.     

Synthesis,characterisation and supramolecular interaction of Rh-biphenylic-imidazole-phenanthroline with antibiotics

A novel rhodium biphenylic imidazole phenanthroline metal-organic complex (BIP-MC) has been synthesised and characterised as a stable supramolecule. The structure of compound was established on the basis ESI, ¹H NMR and UV–vis spectroscopic data. The selectivity of BIP-MC as a new fluorescent chemosensor for various antibiotics has been explored. The supramolecular interaction of amoxicillin with BIP-MC enhanced the fluorescence activity of BIP-MC. A linear response of the sensor was observed in the measuring ranges of excitation 240–298 nm and emission 290–360 nm with detection limits of up to 10 μg/ml at an optimum pH 8.0. Based on the observations made here, a new quantitative method for the determination of this drug in synthetic samples without the use of separation of matrix is developed. It is also inferred that the possible fluorescence enhancement is due to the formation of exciplex between the BIP-MC and amoxicillin. These finding will thus help in pharmacokinetics studies of drugs. The sensor was used for the direct assay of amoxicillin antibiotic in commercial pharmaceutical preparations.     

A New,Mild, and Rapid Transformation of Acylals to Bisulfites in One-Pot Synthesis by Bismuth (III) Nitrate Pentahydrate

Abstract

Direct conversion of acylals to the corresponding bisulfites can be easily performed in the presence of bismuth (III) nitrate pentahydrate in ethanol at room temperature in good yields.     

Highly Regioselective Ring Opening of Epoxides with Thiols Catalyzed by SbCl3 Under Solvent-Free Conditions

The ring-opening reaction of epoxides with thiols by SbCl ₃ supported on Kieselguhr under solvent-free conditions, afforded high yields of β-hydroxy sulfides. Nucleophilic attack of the thiols occurs regioselectively at the less hindered side of the epoxides.     

Phytochemical analysis, cytotoxic activity and constituents-activity relationships of the leaves of Cinnamomum iners (Reinw. ex Blume-Lauraceae)

The leaves of Cinnamomum iners (Reinw. ex Blume-Lauraceae) have been refluxed successively with chloroform and alcohol to get chloroform extract and alcoholic extract. Both the extracts have been assayed for cytotoxicity against human colorectal tumour cells. The chloroform extract exhibited significant cytotoxicity with IC(50) 31?μg mL(-1) (p??200?μg mL(-1). The chloroform extract has been further proceeded for chemical analysis by GC-TOFMS and 178 components were identified including acids, amines, amides, aldehydes, alcohols, esters, benzene derivatives, bicyclic compounds, terpenes, hydrocarbons, naphthalene derivatives, furan derivatives, azulenes, etc. Nine components representing 51.73% of the total chloroform extract were detected as major components. Caryophyllene (14.41%) and Eicosanoic acid ethyl ester (12.17%) are the most prominent components of the chloroform extract. β-Caryophyllene (14.41%) as most abundant compound supports potent cytotoxicity as shown by chloroform extract.     

Synthesis and microstructural study of stereoblock elastomeric polypropylenes from metallocene catalyst (2‐PhInd)2ZrCl2 activated with cocatalyst mixtures

Various elastomeric polypropylenes (PPs) are synthesized through homogeneous propylene polymerization with metallocene catalyst (2‐PhInd)₂ZrCl₂ in the presence of different cocatalyst mixtures: triethylaluminum (TEA)/methylaluminoxane (MAO) or triisobutylaluminum (TIBA)/MAO in the range of Al_AlR3/Al_MAO = 0.0–0.9. The cocatalyst formulation impacts the resultant polymer microstructure and the thermal and dynamic mechanical properties of the produced PPs. ¹³C NMR analysis of the polymers reveals essentially atactic PP, with mmmm = 7.9%, when Al_AlR3/Al_MAO = 0.0. The mmmm pentad content is maximized when Al_AlR3/Al_MAO = 0.8; for TIBA, mmmm = 23.5%; and for TEA, mmmm = 17.6%. Differential scanning calorimetry analysis and dynamic mechanical thermal analysis corroborate these findings. Specifically, T_m, ΔH_m, and T_g are essentially maximized under these conditions, and the minimum damping is observed for Al_AlR3/Al_MAO = 0.6–0.8. ¹H NMR analysis of the mixtures of catalyst and cocatalysts (without monomer) shows very minor differences for [Zr]:Al_AlR3 in the range of 1:1–1:5. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Three-Component,One-Pot Synthesis of Benzo[b][1,4]oxazines in Ionic Liquid 1-Butyl-3-methylimidazolium Bromide

Benzo[b][1,4]oxazines have been synthesized in good to excellent yields in the presence of the ionic liquid 1-butyl-3-methylimidazolium bromide [bmim]Br under relatively mild conditions without any added catalyst, The method offers the advantages of good yields and short reaction times, and the ionic liquid can be easily separated from the product and reused.     

Synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones using nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl2 nanoparticles

Nano‐Zn‐[2‐boromophenyl‐salicylaldimine‐methylpyranopyrazole]Cl₂ (nano‐[Zn‐2BSMP]Cl₂) as a nanoparticle Schiff base complex and a catalyst was introduced for the solvent‐free synthesis of 4‐((2‐hydroxynaphthalen‐1‐yl)(aryl)methyl)‐5‐methyl‐2‐phenyl‐1H‐pyrazol‐3(2H)‐ones by the multicomponent condensation reaction of various aromatic aldehydes, β‐naphthol, ethyl acetoacetate, and phenyl hydrazine at room temperature.