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Combined Experimental (combined + experimental)
Selected AbstractsMechanistic Insights into Acetophenone Transfer Hydrogenation Catalyzed by Half-Sandwich Ruthenium(II) Complexes Containing 2-(Diphenylphosphanyl)aniline , A Combined Experimental and Theoretical StudyEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Alessia Bacchi Abstract Several new half-sandwich ruthenium(II) complexes containing 2-(diphenyphosphanyl)aniline (PNH2) of formula {Ru[(,2P,N)PNH2](p -cymene)Cl}Y [Y = Cl (1a), PF6 (1b), BF4 (1c), BPh4 (1d), TfO (1e)] were synthesized and fully characterized both in solution (1H NMR and 31P{1H} NMR spectroscopy) and in the solid state (FTIR, X-ray analysis on single crystal). Complexes 1a and 1b are active precatalysts in the hydrogen transfer reaction of acetophenone, leading to tof values up to 4440 h,1. In comparison, the {Ru[(,2P,N)PNMe2](p -cymene)Cl}Cl complex leads to a tof value of 100 h,1 under the same catalytic conditions. The mechanism through which the precatalysts operate was deeply explored by high-resolution MS (ESI) and DFT/PCM studies. The results reveal that the complexes containing PNH2 operate through a bifunctional mechanism analogous to that proposed for diamines and amino alcohol ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthetic and Mechanistic Aspects of Acid-Catalyzed Disproportionation of Dialkyl Diarylmethyl Ethers: A Combined Experimental and Theoretical StudyEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 25 2009Margherita Barbero Abstract The disproportionation reactions of various dialkyl diarylmethyl ethers have been carried out in the presence of a catalytic amount (10 mol-%) of o -benzenedisulfonimide as a Brønsted acid catalyst; the reaction conditions were mild, and the yields of the diarylmethane target products were good. The catalyst was easily recovered and purified, ready to be used in further reactions. The theoretical study confirmed that the reaction proceeds in two steps: The formation of a carbocation from the protonated ether followed by hydride transfer. Although the hydride transfer is the rate-determining step, it is the stability of the carbocation that determines the reaction rate and therefore the yields. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] A Combined Experimental and Theoretical Study of Anion,, Interactions in Bis(pyrimidine) SaltsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 35 2007Angel Garcia-Raso Abstract We report the synthesis and X-ray characterization of an N,N, -tetramethylenebis(2-aminopyrimidinium) tetrafluoroborate salt that exhibits anion,, interactions that are responsible for the crystal packing. The anion forms a sandwich complex with two pyrimidine rings. When the anion is nitrate, the crystal packing is governed by anion,, interactions and hydrogen bonds, and the sandwich complex is not formed. Finally, a theoretical study of the anion,, interactions in charged pyrimidine rings is in good agreement with the experimental findings. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] The Cycloaddition Reaction Between ,-Bromo Vinylketenes and Imines: A Combined Experimental and Theoretical StudyADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2008Fides Benfatti Abstract The unusual behaviour of ,-bromo vinylketenes in the cycloaddition reactions with imines is described. This class of vinylketenes behaves as dienophiles in [2+2] reactions, but also displays an unusual diene reactivity in [4+2] reactions. Interestingly, the reactivity of ,-bromo vinylketenes can be modulated via a fine tuning of the substituents. For instance, a methyl group in the ,-position completely inhibits the [2+2] reaction and the [4+2] pathway is almost exclusively followed. A more hindered ketimine (instead of a simple imine) is enough to activate again the [2+2] mechanism. We have carried out a DFT theoretical investigation to rationalise these experimental observations. We have considered two pathways for the [2+2] reaction involving imine, that is, the endo and exo pathways. The former is favoured in the case of ,-bromo vinylketenes, while the latter is preferred for non-substituted vinylketenes. Since the [4+2] cycloaddition becomes possible only when the s - Z -conformation of vinylketene is significantly populated, the presence of bromine substituents in this substrate is crucial in determining the [2+2] or [4+2] mechanisms. For unsubstituted vinylketenes, the barrier connecting the s-E - to the s-Z -conformation is too high to be easily overcome. Thus, the s - Z -structure has a low population and the [2+2] mechanism is favoured. In the case of ,-bromo vinylketenes (especially the ,-methyl-substituted ones), this barrier can be surmounted and the [4+2] mechanism becomes available. [source] Photocatalytic Activity and Electronic Structure Analysis of N-doped Anatase TiO2: A Combined Experimental and Theoretical StudyCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 6 2009H. Gao Abstract N-Doped TiO2 photocatalysts were prepared by a hydrothermal method with tetra- n -butyl titanate (TTNB) and triethanolamine as precursors. The obtained samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-visible diffuse reflectance spectra (DRS), respectively. Photocatalytic activities of the anatase products were investigated on the degradation of methyl orange (MO). The incorporation of nitrogen impurity in anatase TiO2 was studied by the first-principles calculations based on the density functional theory (DFT). The calculated electronic band structures for substitutional and interstitial N-doped TiO2 indicated the formation of localized states in the band gap, which lied above the valence band. Excitation from the impurity states of N 2p to the conduction band could account for the optical absorption edge shift toward the lower energies. It was consistent with the experimentally observed absorption of N-doped samples in the visible region. [source] ChemInform Abstract: Soluble Semiconductors AAsSe2 (A: Li, Na) with a Direct-Band-Gap and Strong Second Harmonic Generation: A Combined Experimental and Theoretical Study.CHEMINFORM, Issue 24 2010Tarun K. Bera Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Uranyl Complexation in Fluorinated Acids (HF, HBF4, HPF6, HTf2N): A Combined Experimental and Theoretical Study.CHEMINFORM, Issue 19 2005Clotilde Gaillard Abstract For Abstract see ChemInform Abstract in Full Text. [source] Bis(oxazoline)titanium Complexes as Chiral Catalysts for Enantioselective Hydrosilylation of Ketones , A Combined Experimental and Theoretical Investigation.CHEMINFORM, Issue 47 2003Marco Bandini Abstract For Abstract see ChemInform Abstract in Full Text. [source] Two Distinct Mechanisms of Alkyne Insertion into the Metal,Sulfur Bond: Combined Experimental and Theoretical Study and Application in CatalysisCHEMISTRY - A EUROPEAN JOURNAL, Issue 7 2010Valentine Abstract The present study reports the evidence for the multiple carbon,carbon bond insertion into the metal,heteroatom bond via a five-coordinate metal complex. Detailed analysis of the model catalytic reaction of the carbon,sulfur (CS) bond formation unveiled the mechanism of metal-mediated alkyne insertion: a new pathway of CS bond formation without preliminary ligand dissociation was revealed based on experimental and theoretical investigations. According to this pathway alkyne insertion into the metal,sulfur bond led to the formation of intermediate metal complex capable of direct CS reductive elimination. In contrast, an intermediate metal complex formed through alkyne insertion through the traditional pathway involving preliminary ligand dissociation suffered from "improper" geometry configuration, which may block the whole catalytic cycle. A new catalytic system was developed to solve the problem of stereoselective SS bond addition to internal alkynes and a cost-efficient Ni-catalyzed synthetic procedure is reported to furnish formation of target vinyl sulfides with high yields (up to 99,%) and excellent Z/E selectivity (>99:1). [source] Regio- and Stereoselective Palladium-Pincer Complex Catalyzed Allylation of Sulfonylimines with Trifluoro(allyl)borates and Allylstannanes: A Combined Experimental and Theoretical StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 26 2006Olov A. Wallner Dr. Abstract Regio- and stereoselective palladium-pincer complex catalyzed allylation of sulfonylimines has been performed by using substituted trifluoro(allyl)borates and trimethylallylstannanes. The reactions provide the corresponding branched allylic products with excellent regioselectivity. The stereoselectivity of these processes is very high when trifluoro(cinnamyl)borate and trimethyl cinnamyl stannane are employed as allylic precursors; however, the reaction with trifluoro(crotyl)borate results in poor stereoselectivity. The major diastereomer formed in these reactions was the syn isomer, while the (previously reported) reactions with aldehyde electrophiles afforded the anti products, indicating that the mechanism of the stereoselection is dependent on the applied electrophile. Therefore, we have studied the mechanistic aspects of the allylation reactions by experimental studies and DFT modeling. The experimental mechanistic studies have clearly shown that potassium trifluoro(allyl)borate undergoes transmetallation with palladium-pincer complex 1,a affording an ,1 -allylpalladium-pincer complex (1,e). The mechanism of the transfer of the allyl moiety from palladium to the sulfonylimine substrate was studied by DFT calculations at the B3PW91/LANL2DZ+P level of theory. These calculations have shown that the electrophilic substitution of sulfonylimines proceeds in a one-step process with a relatively low activation energy. The topology of the potential energy surface in the vicinity of the transition-state structure proved to be rather complicated as nine different geometries with similar energies were located as first order saddle points. Our studies have also shown that the high stereoselectivity with cinnamyl metal reagents stems from steric interactions in the TS structure of the allylation reaction. In addition, these studies have revealed that the mechanism of the stereoselection in the allylation of aldehydes and sulfonylimines is fundamentally different. [source] 103Rh NMR Chemical Shifts in Organometallic Complexes: A Combined Experimental and Density Functional StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2004Laura Orian Dr. Abstract Experimental 103Rh NMR chemical shifts of mono- and binuclear rhodium(I) complexes containing s - or as -hydroindacenide and indacenediide bridging ligands with different ancillary ligands (1,5-cyclooctadiene, ethylene, carbonyl) are presented. A protocol, based on density functional theory calculations, was established to determine 103Rh NMR shielding constants in order to rationalise the effects of electronic and structural variations on the spectroscopic signal, and to gain insight into the efficiency of this computational method when applied to organometallic systems. Scalar and spin,orbit relativistic effects based on the ZORA (zeroth order regular approximation) level have been taken into account and discussed. A good agreement was found for model compounds over a wide range of chemical shifts of rhodium (,10,000 ppm). This allowed us to discuss the experimental and calculated ,(103Rh) in larger complexes and to relate it to their electronic structure. [source] Oligophenylenevinylenes in Spatially Confined Nanochannels: Monitoring Intermolecular Interactions by UV/Vis and Raman Spectroscopy,ADVANCED FUNCTIONAL MATERIALS, Issue 6 2008Mariya Aloshyna Abstract Perhydrotriphenylene-based channel-forming inclusion compounds (ICs) and thin films made of polyphenylenevinylene (PPV)-type oligomers with terminal alkoxy groups are investigated and compared in a combined experimental and theoretical approach. Interchromophore interactions and host-guest interactions are elucidated by UV/Vis and Raman spectroscopy. The impact of the local environment of the chromophore on the optical and photophysical properties is discussed in light of quantum-chemical calculations. In stark contrast to thin films where preferential side-by-side orientation leads to quenching of photoluminescence (PL) via non-emissive traps, the ICs are found to be attractive materials for opto-electronic applications: they offer high chromophore concentrations, but at the same time behave as quasi-isolated entities of tightly packed, well-oriented objects with high PL quantum yields and the possibility of color tuning. [source] 4-Acetoxystyrene nitroxide-mediated controlled radical polymerization: Comparison with styreneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2010Andrew S. Cho Abstract The nitroxide-mediated controlled radical polymerization (NM-CRP) of 4-acetoxystyrene with an alkoxyamine was analyzed by a combined experimental and modeling approach. At low nitroxide concentrations, thermal initiation was significant, and control of the polydispersity was poor, as was observed previously for styrene. A continuum model based on the method of moments was used to regress the parameters for the reversible nitroxide uncoupling/coupling reactions (activation energy of uncoupling), thermal initiation (activation energy of initiation), and termination (frequency factor of recombination). The model was able to capture the molecular weight averages and the polydispersity index as a function of time and the nitroxide concentration qualitatively and quantitatively. Using this mechanistic framework, we developed kinetic Monte Carlo models that allowed the molecular weight distributions to be predicted explicitly in good agreement with experimental data. A comparison of the NM-CRP of 4-acetoxystyrene and styrene is provided to illustrate the effect of the acetoxy substituent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Structural Effects on the Electronic Absorption Properties of 5,6-Dihydroxyindole Oligomers: The Potential of an Integrated Experimental and DFT Approach to Model Eumelanin Optical Properties,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 3 2008Marco D'Ischia Elucidation of the relationships between structural features and UV,visible absorption properties of 5,6-dihydroxyindole oligomers is an essential step towards an understanding of the unique optical properties of eumelanins. Herein, we report the first combined experimental and density functional theory (DFT) investigation of the 5,6-dihydroxyindole oligomers so far isolated. 2,2,-Biindolyl 2 and the 2,4,-biindolyl 3 absorb at longer wavelengths relative to 2,7,-biindolyl 4 and their spectra were well predicted by DFT analysis. The absorption bands of 2,4,:2,,4,,- and 2,4,:2,,7,,-triindolyls 5 and 6 also fall at different wavelengths and can be interpreted by DFT simulations as being due to a combination of two main separate transitions. Tetramer 7, in which two 2,4,-biindolyl units are linked through a 2,3,-connection, exhibits a broad chromophore extending over the entire UV range without well defined absorption maxima. Within the dimer,tetramer range examined, three key points emerge: (1) an increase in oligomer chain length does not result in any regular and predictable bathochromic shift; (2) a marked broadening of the absorption bands occurs when going from the monomer to the tetramer structure; and (3) the mode of coupling of the indole units is a crucial, hitherto unrecognized, structural parameter affecting the electronic absorption properties of 5,6-dihydroxyindole oligomers. It is concluded that use of experimentally characterized oligomeric scaffolds as a basis for DFT calculations is a most promising approach to building reliable structural models for studies of eumelanins optical properties. [source] Tracking large solid constructs suspended in a rotating bioreactor: A combined experimental and theoretical studyBIOTECHNOLOGY & BIOENGINEERING, Issue 6 2009L.J. Cummings Abstract We present a combined experimental and theoretical study of the trajectory of a large solid cylindrical disc suspended within a fluid-filled rotating cylindrical vessel. The experimental set-up is relevant to tissue-engineering applications where a disc-shaped porous scaffold is seeded with cells to be cultured, placed within a bioreactor filled with nutrient-rich culture medium, which is then rotated in a vertical plane to keep the growing tissue construct suspended in a state of "free fall." The experimental results are compared with theoretical predictions based on the model of Cummings and Waters (2007), who showed that the suspended disc executes a periodic motion. For anticlockwise vessel rotation three regimes were identified: (i) disc remains suspended at a fixed position on the right-hand side of the bioreactor; (ii) disc executes a periodic oscillatory motion on the right-hand side of the bioreactor; and (iii) disc orbits the bioreactor. All three regimes are captured experimentally, and good agreement between theory and experiment is obtained. For the tissue engineering application, computation of the fluid dynamics allows the nutrient concentration field surrounding a tissue construct (a property that cannot be measured experimentally) to be determined (Cummings and Waters, 2007). The implications for experimental cell-culture protocols are discussed. Biotechnol. Bioeng. 2009; 104: 1224,1234. © 2009 Wiley Periodicals, Inc. [source] Cyclometalated IrIII Complexes with Substituted 1,10-Phenanthrolines: A New Class of Efficient Cationic Organometallic Second-Order NLO ChromophoresCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2010Adriana Valore Dr. Abstract Cyclometalated cationic IrIII complexes with substituted 1,10-phenanthrolines (1,10-phen), such as [Ir(ppy)2(5-R-1,10-phen)]Y (ppy=cyclometalated 2-phenylpyridine; R=NO2, H, Me, NMe2; Y,=PF6,, C12H25SO3,, I,) and [Ir(ppy)2(4-R,7-R-1,10-phen)]Y (R=Me, Ph) are characterized by a significant second-order optical non linearity (measured by the electrical field induced second harmonic generation (EFISH) technique). This nonlinearity is controlled by MLCT processes from the cyclometalated IrIII, acting as a donor push system, to ,* orbitals of the phenanthroline, acting as an acceptor pull system. Substitution of cyclometalated 2-phenylpyridine by the more , delocalized 2-phenylquinoline (pq) or benzo[h]quinoline (bzq) or by the sulfur-containing 4,5-diphenyl-2-methyl-thiazole (dpmf) does not significantly affect the ,, absolute value, which instead is affected by the nature of the R substituents on the phenanthroline, the higher value being associated with the electron-withdrawing NO2 group. By using a combined experimental (the EFISH technique and 1H and 19F PGSE NMR spectroscopy) and theoretical (DFT, time-dependent-DFT (TDDFT), sum over states (SOS) approach) investigation, evidence is obtained that ion pairing, which is controlled by the nature of the counterion and by the concentration, may significantly affect the ,, values of these cationic NLO chromophores. In CH2Cl2, concentration-dependent high absolute values of ,, are obtained for [Ir(ppy)2(5-NO2 -1,10-phen)]Y if Y is a weakly interacting anion, such as PF6,, whereas with a counterion, such as C12H25SO3, or I,, which form tight ion-pairs, the absolute value of ,, is lower and quite independent of the concentration. This ,, trend is partially due to the perturbation of the counterion on the LUMO ,* levels of the phenanthroline. The correlation between the ,, value and dilution shows that the effect of concentration is a factor that must be taken into careful consideration. [source] Progress in the Understanding of Drug,Receptor Interactions, Part,2: Experimental and Theoretical Electrostatic Moments and Interaction Energies of an Angiotensin II Receptor Antagonist (C30H30N6O3S)CHEMISTRY - A EUROPEAN JOURNAL, Issue 24 2007Raffaella Soave Dr. Abstract A combined experimental and theoretical charge density study of an angiotensin II receptor antagonist (1) is presented focusing on electrostatic properties such as atomic charges, molecular electric moments up to the fourth rank and energies of the intermolecular interactions, to gain an insight into the physical nature of the drug,receptor interaction. Electrostatic properties were derived from both the experimental electron density (multipole refinement of X-ray data collected at T=17,K) and the ab initio wavefunction (single molecule and fully periodic calculations at the DFT level). The relevance of S,,,O and S,,,N intramolecular interactions on the activity of 1 is highlighted by using both the crystal and gas-phase geometries and their electrostatic nature is documented by means of QTAIM atomic charges. The derived electrostatic properties are consistent with a nearly spherical electron density distribution, characterised by an intermingling of electropositive and -negative zones rather than by a unique electrophilic region opposed to a nucleophilic area. This makes the first molecular moment scarcely significant and ill-determined, whereas the second moment is large, significant and highly reliable. A comparison between experimental and theoretical components of the third electric moment shows a few discrepancies, whereas the agreement for the fourth electric moment is excellent. The most favourable intermolecular bond is show to be an NH,,,N hydrogen bond with an energy of about 50,kJ,mol,1. Key pharmacophoric features responsible for attractive electrostatic interactions include CH,,,X hydrogen bonds. It is shown that methyl and methylene groups, known to be essential for the biological activity of the drug, provide a significant energetic contribution to the total binding energy. Dispersive interactions are important at the thiophene and at both the phenyl fragments. The experimental estimates of the electrostatic contribution to the intermolecular interaction energies of six molecular pairs, obtained by a new model proposed by Spackman, predict the correct relative electrostatic energies with no exceptions. [source] Effect of Polarity and Structural Design on Molecular Photorefractive Properties of Heteroaromatic-Based Push,Pull DyesCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2006Graziano Archetti Dr. Abstract A combined experimental (optical and electro-optical absorption measurements) and computational (ab initio RHF and DFT) approach has been used to investigate the molecular low- and high- Tg photorefractive (PR) performances of neutral and zwitterionic heteroaromatic dipolar chromophores in terms of structural and solvent-polarity effects. We have found that the nature of the building units (donor, acceptor, and spacer) and the polarity of the surrounding medium strongly affect all the relevant ground-state and nonlinear optical properties involved in the PR activity, that is, the dipole moment, the polarizability anisotropy, and first hyperpolarizability of the electronic ground-state. The variation of these properties is in turn transferred to molecular low- and high- Tg PR figures of merit. It is shown that PR molecular performance not only relies on a proper choice of structural components but varies by orders of magnitude as a function of the medium polarity, and this suggests that a combination of molecular design and host-matrix engineering is required for optimized performances of PR materials. [source] | ||||||||||||||||