COSY NMR Spectroscopy Research Articles

Aqueous emissive cyclometalated iridium photoreductants: synthesis, computational analysis and the photocatalytic reduction of 4-nitrophenol.

Herein, we present luminescent mononuclear iridium complexes [1]3+-[4]3+ using NEt3-appended C^N chelating benzimidazole (L1-L4) and semi-flexible phenanthroline-pyrazine-based (phpy) ligands exhibiting photocatalytic reduction of 4-nitrophenol (4-NP) in the presence of NEt3 in an aqueous medium. The formation of [1]3+-[4]3+ was confirmed by HRMS, 1H-1H COSY, and 13C and 19F NMR spectroscopy. The complex [4]3+ is water soluble, whereas the others ([1]3+-[3]3+) are partially soluble. The complexes are luminescent in both CH3CN and H2O media. The DFT study reveals that the HOMO of [1]3+ resides on the C^N chelating benzimidazole and iridium center. However, it moves to the pyrazine-pyridine of the phpy unit in the case of [2]3+-[4]3+. The LUMOs are localized on the phenanthroline unit of phpy for all the complexes. This suggests an important role of the fluorine atom on electron density distribution. Spin density analysis demonstrates that the emission bands of the complexes arise from 3MLLCT states. The complex [4]3+ displays promising photocatalytic activity towards 4-NP photoreduction, whereas complexes [1]3+-[3]3+ exhibit lower reactivity. The mechanistic study suggests that the reaction proceeds through an oxidative quenching pathway, where 4-NP is reduced by accepting an electron from excited [Ir(III)] and gets oxidized to Ir(IV), which comes back to its original Ir(III) state by accepting an electron from the sacrificial electron donor NEt3.

Synthesis, Structure and Antiradical Activity of Functionally Substituted Hydrazides of Isonicotinic Acid

The purpose of this work is the synthesis of new isonicotinic acid hydrazones, the study of their structure, reactivity and biological screening of some synthesized compounds. The reactions leading to new N-arylidene(alkylidene) hydrazones via the condensation of isonicotinic acid hydrazide with various derivatives of aromatic aldehydes were studied. The structure of the new functionally substituted isonicotinic acid hydrazones was established by FTIR, 1H and 13C NMR, two-dimensional COSY (1H-1H) NMR spectroscopy and HMQC (1H-13C). The antiradical activity of the synthesized derivatives was studied using diphenylpycrylhydrazide radical (DPPH) assay. It was shown that N-(3- ethoxy-4-hydroxybenzylidene)isonicotinohydrazide possesses antiradical activity (IC50 (DPPH) 103.0 μM). The antiradical properties of compounds of phenolic nature are in agreement with the energies of homolytic O-H bond dissociation calculated with the use of density functional theory.

Friedel-Crafts Reaction of Vinyltrimethoxysilane with Styrene and Composite Materials on Their Base

Friedel-Crafts alkylation reaction of vinyltri-methoxysilane with styrene was performed in the pres-ence of anhydrous AlCl3. Alkoxy(4-vinylphenethyl)silane has been obtained. The synthesized products were identified by 1H, 13C, COSY NMR, and FTIR spectroscopy. Calculations using the quantum-chemical non-empirical density functional theory (DFT) method for the reaction between vinyltrimethoxysilane and styrene performed for ortho-, meta- and para-positions were discussed. For the theoretical modeling an online prediction program "Priroda 04: A quantum-chemical program suite" was used. Composite materials based on wood sawdust with various dispersion qualities and synthesized trimethoxysilylated styrene as a binding and reinforcing agent with degrees of silylation (5 %), in the presence of various organic/inorganic additives, fire retardants, and antioxidants, have been developed at different temperatures and pressures via hot press method or extrusion. The physico-mechanical properties of composites have been investigated.

Solvent-dependent selective “naked eye” chromofluorogenic multifunctional rhodamine-based probe for Al3+, Cu2+, Hg2+, S2− and CN− ions

The solvent-dependent selective “naked eye” chromofluorogenic multifunctional rhodamine-based probe 3 for Al3+, Cu2+, Hg2+, S2− and CN− ions was synthesized and its spectral, luminescent and ionochromic properties were studied. The compound obtained exists in the spirolactam form, confirmed by data of 1H, COSY, HSQC, HMBC and 13C NMR spectroscopy. In ethanol, Al3+ ions selectively, even in the presence of other metal cations (Na+, Ba2+, Zn2+, Cd2+, Ni2+, Co2+, Cu2+, Hg2+ and Fe3+) initiate the opening of the spirolactam ring, accompanied by the appearance of a new absorption band at 556 nm and the “naked eye” effect with a change in the yellow-green color of the solution to orange-pink. At the same time, the initial fluorescence 3 at 539 nm shifts to the longer 579 nm spectral region. The use of acetone as a solvent allows the selective detection of copper(II) cations that turn the yellow color of a solution of 3 to pink-purple (λabs 563 nm) due to the formation of the ring-open complex 3.Cu2+ that exhibits emission at 580 nm. Selective detection of Hg2+ in acetonitrile results in the “naked eye” effect characterized by a change in the color of the solution from bright yellow to pink-cherry (λabs 564 nm). The fluorescence of the mercury(II) complex is observed at 587 nm. Complexes 3.Cu2+ and 3.Hg2+ were used for the sequential selective recognition of S2− and CN− anions, respectively. A combinatorial molecular logic gate was designed based on the cation/anion sensing ability of probe 3.

Free radical polymerization of allylamine in different acidic media

The complex formation between allylamine and mineral acids (HCl, H2SO4, H3PO4) and their stabilities were investigated by Uv-Vis, DSC and TGA analyses. Free radical polymerization of allylamine salts was achieved by using 2,2′-azobis (2-methylpropanediamine)dihydrochloride at 50oC under N2 atmosphere in water. PAlAm synthesized in the presence of H2SO4 and H3PO4 were insoluble in water due to physical crosslinking of chains. They were converted to water soluble PAlAm.HCl by HCl treatment for further characterization. The structures of polymers obtained were elucidated by FT-IR, 1H NMR, 13C, and Cosy NMR spectroscopies. Thermal stability and glass transition behaviors were investigated by TGA and DSC. Tg was found to be 225°C for poly (AlAm.HCl) whereas 23°C for poly (AlAm). The poly (AlAm) showed very high heat stability with no weight loss until 440°C in nitrogen atmosphere. The molecular weight of PAlAm.HCl was determined by 1H NMR and viscosimetry to be 16,000 and 12,000 respectively.

Electrochemically Induced Dimerization of p9mp-C70(CF3)12 Trifluoromethylated Fullerene.

We report a comprehensive study of a novel isomer of C70(CF3)12, p9mp-C70(CF3)12, whose electrochemical behavior differs from most of the other trifluoromethylated fullerenes. The addition pattern of p9mp-C70(CF3)12 is established by means of 19F-19F COSY NMR spectroscopy and DFT calculations. Like p7mp-C70(CF3)10, the new isomer p9mp-C70(CF3)12 undergoes dimerization to the [C70(CF3)12]22- upon single-electron reduction. The electrochemical observations are supported by the DFT calculations of dimerization energy and the temperature dependence of the CW X-band EPR spectroscopy data. Experimentally determined dimerization energies of p9mp-C70(CF3)12-• and p7mp-C70(CF3)10-• in solution are ca -8 and -26 kJ mol-1, respectively, in good correspondence with DFT data.

Characterization of the Structure of 2-(4-methyl-2 Phenyl-4, 5-dihydrooxazol-4-ylmethyl)-isoindole-1, 3-dione by 1D, COSY and HSQC 2D NMR Spectroscopy

The identity of the 2-(4-Methyl-2-phenyl-4,5-dihydrooxazol-4-ylmethyl)-isoindole-1,3-dione, previously synthesized in our laboratory, was proven without doubt by means of 1D and 2D NMR spectroscopy. Two-dimensional NMR spectroscopy played a major role. The analysis of the 2D-COSY spectrum of isoindoline-1,3-dione derivative shows a perfect correlation between neighboring protons. Thus, a correlation was noted between the protons of the phthalimide, H(8) and H(9) on the one hand and H(8') and H(9') on the other hand. The analysis of the 2D-HSQC spectrum of the studied compound indicates a faultless correlation between protons and adjacent carbons, and no correlation in the case of all quaternary carbons.

A novel route for the synthesis of pseudopolyrotaxane containing γ-Cyclodextrin based on environmental waste recycling

The disposal of environmentally harmful waste is one of the most important challenges nowadays, especially when it is turned into important products for the industry. In this perspective, pseudopolyrotaxane containing gamma-cyclodextrin was synthesized for the first time from polystyrene waste recycling. Initially, polystyrene sulfonic acid (1) was facilely obtained in good yield by sulphonation of styrofoam (expanded polystyrene, EPS). Thereafter, it was used to synthesis of pseudopolyrotaxane (2). The chemical structure of the newly synthesized polymers (1) and (2) was established by their spectral analysis such as FT-IR, 1H-, 13C-, and cosy-NMR spectroscopy. The surface morphology and the thermal stability of these two polymers were investigated by scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA), respectively. The optical properties of compounds (1) and (2) were also explored. The results confirmed that the promising new strategy of the synthesis process based on modifying polystyrene sulfonic acid by encapsulation of γ –cyclodextrin significantly enhanced the thermal stability and the optical properties of the final product making it suitable for a wide range of industrial uses.

Synthesis and structure of 9-hydroxy-1,2-dicarba-closo-dodecaborane(11)

The oxidation of 1,2-C2B10H12 (1) with 100% nitric acid was studied in two solvents (CH2C12 and CCl4). Under the action of superacid (CF3SO3H), the compound 9-HO-1,2-C2B10H11 (2) gives the onium cation 9-H2O+-1,2-C2B10H11 involved in the salt [9-H2O+-1,2-C2B10Hn]-CF3SO3???, as demonstrated by uB NMR spectroscopy. The experimental and simulated uB NMR spectra of the cation 9-H2O+-1,2-C2B10H11 are in satisfactory agreement with each other. In the presence of a base, compound 2 is transferred from an ethereal solution to an aqueous alkaline solution giving the anion 9-O???- 1,2-C2B10H11. The structure of compound 2 was confirmed by 1H, 11B, 11B1H, 11B-11B COSY NMR spectroscopy, IR spectroscopy, and gas chromatography mass spectrometry and was additionally established by X-ray diffraction.

Synthesis and characterisation of a partially methylated dodecyl thiomaltotrioside derivative as a precursor of cyclodextrin analogue

Due to the enermous roles of cyclodextrin combining with small organic molecules, more recent interests study about the manipulation of cyclodextrin structure giving better performance for any kinds of field but they presented long synthetis steps as producing the precursors. This study points out the synthesis of precursor of β-cyclodextrin analouges with maltotriose as raw materials giving the short synthesis steps. The product structures were analysed by Fourier Transform Infrared (FTIR) Specstroscopy,and characterised by 1H-, 13C- NMR, COSY NMR, and ESI Mass Spectroscopy. The result showed that O-acetylation reaction produced maltotriose derivative 1 (95%), thioglycosidation reaction produced maltotriose derivative 2 (54%), de-acetylation reaction produced maltotriose derivative 3 (97%), O-benzylidation reaction produced a mixture of maltotriose derivatives 4, O- methylation reaction produced maltotriose derivative 5 (46%) and de-benzylidation reaction produced maltotriose derivative 6 (85%).

Pumping a Ring-Sliding Molecular Motion by a Light-Powered Molecular Motor.

Designing artificial molecular machines to execute complex mechanical tasks, like coupling rotation and translation to accomplish transmission of motion, continues to provide important challenges. Herein, we demonstrated a novel molecular machine comprising a second-generation light-driven molecular motor and a bistable [1]rotaxane unit. The molecular motor can rotate successfully even in an interlocked [1]rotaxane system through a photoinduced cis-to -trans isomerization and a thermal helix inversion, resulting in concomitant transitional motion of the [1]rotaxane. The transmission process was elucidated via 1H NMR, 1H-1H COSY, HMQC, HMBC, and 2D ROESY NMR spectroscopies, UV-visible absorption spectrum, and density functional theory calculations. This is the first demonstration of a molecular motor to rotate against the appreciably noncovalent interactions between dibenzo-24-crown-8 and N-methyltriazolium moieties comprising the rotaxane unit, showing operational capabilities of molecular motors to perform more complex tasks.

Spectroscopic Investigation of Thermochemical Depolymerization of Lignin Model Compounds in the Presence of Novel Liquidlike Nanoparticle Organic Hybrid Solvents for Efficient Biomass Valorization

This study reports the thermochemical transformation of lignin model compounds using nanoparticle organic hybrid materials (NOHMs). NOHMs have recently been developed as an emerging class of self-suspended nanoparticle solvent systems created by ionically or covalently grafting organic oligomers or polymers (canopy) onto surface-modified inorganic nanoparticles (core). Because NOHMs exhibit negligible vapor pressure with the ability to tailor physicochemical properties, they could be a promising catalytic solvent for the lignin thermochemical conversion process. The thermochemical conversion of lignin model compounds was achieved with the synthesized NOHM at an elevated temperature of 473 K, and the results were compared with the case of the ionic liquid [EMIM][ESO4]. The fractured moieties of the lignin model compounds were qualitatively identified by ATR FT-IR and 2D COSY NMR spectroscopies. The results indicated that the NOHM decomposed the C–O and/or C–C bonds of lignin model chemicals more efficientl...

Synthesis and Characterization of Carboxyethylated Lignosulfonate.

Lignosulfonate is a byproduct of the sulfite pulping process and has limited use in industry. The main objective of this study was to investigate the carboxyethylation of lignosulfonate to increase its charge density to broaden its applications. The carboxyethylation of lignosulfonate was optimized under the conditions of 30 wt % NaOH, 2.0 mol mol-1 2-chloropropinic acid/lignosulfonate, 90 °C, 0.5 h, and 0.03 mol 2-chloropropinic acid, which produced carboxyethylated lignosulfonate with a charge density and molecular weight of -3.51 meq g-1 and 46 493 g mol-1 , respectively. The mechanism of the carboxyethylation reaction using 2-chloropropinic acid by an SN 1 pathway in an alkaline solution was discussed. Methylation was also used to mask the phenolic hydroxide groups of lignosulfonate to investigate if carboxyethylation occurred on aliphatic hydroxide groups of lignosulfonate. The produced carboxyethylated lignosulfonate was characterized by using FTIR spectroscopy, NMR spectroscopy, gel permeation chromatography, and elemental and functional group analyses. Basic 1 H-1 H 2 D COSY NMR spectroscopy was used to record the coupled spins of the carboxyethyl group on carboxyethylated lignosulfonate. The information from 1 D 1 H NMR and 2 D NMR COSY spectroscopy provided evidence for the existence of a 1-carboxyethyl group on the carboxyethylated lignosulfonate structure.

Molecular recognition of flunarizine dihydrochloride and \u03b2-cyclodextrin inclusion complex by NMR and computational approaches

BackgroundFlunarizine dihydrochloride (FLN) is used in the prophylactic treatment of migraine, vertigo, occlusive peripheral vascular disease and epilepsy. Cyclodextrins (CDs) are chiral, truncated cone shaped macrocycles known for their inner hydrophobic and outer hydrophilic site. They form complexes with hydrophobic drug molecules and enhance the solubility and bioavailability of such compounds by enhancing drug permeability through mucosal tissues. NMR spectroscopy and computational docking have been recognized as an important tool for the interaction study of CDs-drug inclusion complexes in solution state.ResultsThe structural assignments of FLN and β-CD protons were determined by 1H NMR and 2D 1H-1H COSY NMR spectroscopy. 1H NMR spectroscopic studies of FLN, β-CD and their mixtures confirmed the formation of β-CD-FLN inclusion complex in solution. 1H NMR titration data for β-CD-FLN inclusion complex showed 1:1 stoichiometry, an association constant of Ka = 157 M−1 and change in Gibbs free energy of ∆G = − 12.65 kJ mol−1. The binding constant of the β-CD inclusion complex with two nearly similar structures, FLN and cetirizine dihydrochloride, were compared. Two-dimensional 1H-1H ROESY spectral data and molecular docking studies showed the modes of penetration of the aromatic rings from the wider rim side into the β-CD cavity. The possible geometrical structures of the β-CD-FLN inclusion complex have been proposed in which aromatic rings protrude close to the narrower rim of the β-CD truncated cone.ConclusionNMR spectroscopic studies of FLN, β-CD and FLN:β-CD mixtures confirmed the formation of 1:1 inclusion complex in solution at room temperature. Two-dimensional 1H-1H ROESY together with molecular docking study confirmed that the F-substituted aromatic ring of FLN penetrates into β-CD truncated cone and the tail of aromatic rings were proximal to narrower rim of β-CD. The splitting of aromatic signals of FLN in the presence of β-CD suggests chiral differentiation of the guest FLN by β-CD.

Radical scavenging potential, antiinflammatory and antiarthritic activity of isolated isomer Methyl-γ-Orsellinate and roccellatol from Roccella montagnei Bel

The burden of multiple drug resistance towards chronic diseases is rapidly increasing globally at an alarm rate. The present study aims to isolate active principles via bioassay guided fractionation of traditionally used lichen Roccella montagnei for in vitro radical scavenging activity with potential to combat arthritis and inflammation. The results of proximate composition and mineral analysis revealed the presence of essential amount of micro and macro nutrients which are required for secondary metabolite production. Fractions of Roccella montagnei and pure compounds were assessed for its in vitro antioxidant (DPPH, FRAP, OH radical, SOD, CAT, GPX), antiarthritic and antiinflammatory activity. The results indicates that lichen sample and fractions exhibited potent radical scavenger demonstrated in vitro antiarthritic and antiinflammatory activity in dose dependent manner. Bioassay fractionation lead to isolation of two pure compounds ie., Compound I and Compound II which were characterized using spectral data such as FT-IR, 1H NMR, 13C NMR, DEPT NMR spectroscopy, COSY & HMQC NMR spectroscopy and LC-MS analysis and was identified as Methyl-γ-Orsellinate (C9H10O4) a novel isomer from fractions E2d5a with a molecular weight of 182.2 and Roccellatol (C12H16O7) from fractions D3d4c with a molecular weight of 272.3. The present findings suggest that the secondary metabolites present in the lichens have direct relation, with biological activities revealing different properties and can be a future novel antioxidant and a potent anti-arthritic agent.

Self-Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate.

High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H2 F6 NaW18 O56 ]7- from simple tungstate Na2 WO2 F4 was demonstrated by using 2D 19 F-19 F NOESY, 2D 19 F-19 F COSY NMR spectroscopy, a new 2D 19 F{183 W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions.

Dramatic Differences in Aggregation-Induced Emission and Supramolecular Polymerizability of Tetraphenylethene-Based Stereoisomers.

Geometric (Z)- and (E)-isomers play important but different roles in life and material science. The design of new (Z)-/(E)- isomers and study of their properties, behaviors, and interactions are crucially important in molecular engineering. However, difficulties with their separation and structure confirmation limit their structural diversity and functionality in scope. In the work described herein, we successfully synthesized pure isomers of ureidopyrimidinone-functionalized tetraphenylethenes ((Z)-TPE-UPy and (E)-TPE-UPy), featuring both the aggregation-induced emission characteristic of tetraphenylethene and the supramolecular polymerizability of ureidopyrimidinone. Their structures were confirmed by 2D COSY and NOESY NMR spectroscopies. The two isomers show distinct fluorescence in the aggregate state: (Z)-TPE-UPy exhibits green emission, while its (E)-counterpart is blue-emitting. The cavity formed by the two ureidopyrimidinone groups of (Z)-TPE-UPy makes it suitable for Hg2+ detection, and the high-molecular-weight polymers prepared from (E)-TPE-UPy can be used to fabricate highly fluorescent fibers and 2D/3D photopatterns from their chloroform solutions.

Structural elucidation of a water-soluble polysaccharide isolated from Balangu shirazi (Lallemantia royleana) seeds

A novel water-soluble polysaccharide was isolated from the seeds of Balangu shirazi (BSG) by warm-water extraction and then purified. The BGG contained 8.2% moisture, 13.1% ash, 1.6% protein and 77.1% carbohydrate. However, no lipid content was observed. Elemental analysis of the gum indicated BSG had a carbon, hydrogen, oxygen and nitrogen content of 33.39%, 4.05%, 35.45% and 0.31%, respectively. The FT-IR spectroscopy revealed the major functional groups consisted of (OH), (C-H) and (-COO-), and BSG was comprised of pyranose-form sugars with both α-and β-configurations. Monosaccharide composition analysis by GC-MS showed the BSG contained sugar constituents of arabinose, rhamnose, mannose, fructose, galactose, α-and β-d-glucose, glucuronic acid, galacturonic acid, and glucosamine although mainly composed of rhamnose, galactose, arabinose and galacturonic acid. 1H, 13C and COSY NMR spectroscopy demonstrated the presence of (1 → 4)-linked-α-D-GalpA, (1 → 3)-linked-β-D-Galp, (1 → 6)-linked-β-D-Galp, (1 →)-β-L-Arap, (1 → 2)-linked-α-L-Rhap and (1 → 3)-linked-β-L-Arap in the polysaccharide sequence.

Syntheses of Halogenated Polyhedral Phosphaboranes: Crystal Structure of conjuncto‐3,3′‐(closo‐1,2‐P2B4Br3)2

Co‐pyrolysis of B2Br4 with PBr3 at 480 °C gave, in addition to the main product closo‐1,2‐P2B4Br4, conjuncto‐3,3′‐(1,2‐P2B4Br3)2 (1) and the twelve‐vertex closo‐1,7‐P2B10Br10 (2), both in low yields. X‐ray structure determination for 1 [triclinic, space‐group P1 with a = 7.220(2) Å, b = 7.232(2) Å, c = 8.5839(15) Å, α = 97.213(15)°, β = 96.81(2)°, γ = 94.07(2)° and Z = 1] confirmed that 1 adopts a structure consisting of two symmetrically boron–boron linked distorted octahedra with the bridging boron atoms in the 3,3′‐positions and the phosphorus atoms in the 1,2‐positions. The intercluster 2e/2c B–B bond length is 1.61(3) Å. The shortest boron–boron bond within the cluster framework is 1.68(2) Å located between the boron atoms antipodal to the phosphorus atoms. The icosahedral phosphaborane 2 was characterized by 11B‐11B COSY NMR spectroscopy showing cross peaks indicative for the isomer with the phosphorus atoms in 1,7‐positions. Both the X‐ray data of 1 and the NMR spectroscopic data of 1 and 2 give further evidence for the influence of an antipodal effect of heteroatoms to cross‐cage boron atoms and, vice versa, of an additional shielding of the phosphorus atoms caused by B‐Hal substitution at the boron positions trans to phosphorus.

(S)-2-[(N-arylamino)methyl]pyrrolidines-Based PhosphoramiditeP,N-Ligand Library for Asymmetric Metal-Catalyzed Allylic Substitution and Conjugate 1,4-Addition

A library of easy-to-prepare and modular chiral P,N-phosphoramidites based on [1,1′-biaryl]-2,2′-diols and C1-symmetric 1,2-diamines has been designed and developed. The structures of the novel ligands have been elucidated by means of 2D-NMR and confirmed in the solid state by X-ray diffraction analysis. Stereoselectors of this type exhibited high enantioselectivities in Pd-catalyzed allylic substitution reactions of (E)-1,3-diphenylallyl acetate with NaSO2pTol (up to 91 % ee), CH2(CO2Me)2 (up to 89 % ee), (C3H7)2NH (up to 94 % ee) and (EtO)2P(O)CH2NH2 as a novel nucleophile (up to 98 % ee). Ee values of up to 88 % and 72 % have been obtained in the Pd-catalyzed desymmetrization of N,N′-ditosyl-meso-cyclopent-4-ene-1,3-diol biscarbamate and in the Cu-catalyzed 1,4-conjugate addition of diethylzinc to chalcone, respectively. The reactions of P,N-bidentate ligands with [Pd(Cod)Cl2] at molar ratios of L/M=1 and 2 have been studied using 1H, 13C, 13C-1H HSQC, 13C-1H HMBC, 1H-1H COSY, 1H-1H ROESY, DOSY and 31P NMR spectroscopy as well as HR ESI mass spectrometry.