scholarly journals Zn(II)-to-Cu(II) Transmetalation in an Amide Functionalized Complex and Catalytic Applications in Styrene Oxidation and Nitroaldol Coupling

Molecules ◽  
2020 ◽  
Vol 25 (11) ◽  
pp. 2644 ◽  
Author(s):  
Anup Paul ◽  
Luísa M. D. R. S. Martins ◽  
Anirban Karmakar ◽  
Maxim L. Kuznetsov ◽  
M. Fátima C. Guedes da Silva ◽  
...  
Keyword(s):  
Density Functional ◽  
Coupling Reaction ◽  
X Ray Diffraction ◽  
Styrene Oxidation ◽  
Aqueous Hydrogen Peroxide ◽  
Functional Theory ◽  
Catalytic Activities ◽  
Eds Analysis ◽  
Carboxylate Groups ◽  
Thermodynamic Feasibility

The mononuclear zinc(II) complex cis-[ZnL2(H2O)2] (1; L = 4-(pyridin-3-ylcarbamoyl)benzoate) was synthesized and characterized. By soaking crystals of 1 in a mixture of DMF-H2O solution containing a slight excess of Cu(NO3)2 × 3H2O a transmetalation reaction occurred affording the related copper(II) complex trans-[CuL2(H2O)2] (2). The structures of the compounds were authenticated by single crystal X-ray diffraction revealing, apart from a change in the isomerism, an alteration in the relative orientation of the chelating carboxylate groups and of the pyridine moieties. H-bond interactions stabilize both geometries and expand them into two-dimensional (2D) networks. The transmetalation was confirmed by SEM–EDS analysis. Moreover, the thermodynamic feasibility of the transmetalation is demonstrated by density-functional theory (DFT) studies. The catalytic activities of 1 and 2 for the oxidation of styrene and for the nitroaldol (Henry) C-C coupling reaction were investigated. The copper(II) compound 2 acts as heterogeneous catalyst for the microwave-assisted oxidation of styrene with aqueous hydrogen peroxide, yielding selectively (>99%) benzaldehyde up to 66% of conversion and with a turnover frequency (TOF) of 132 h−1. The zinc(II) complex 1 is the most active catalyst (up to 87% yield) towards the nitroaldol (Henry) coupling reaction between benzaldehyde and nitro-methane or -ethane to afford the corresponding β-nitro alcohols. The reaction of benzaldehyde with nitroethane in the presence of 1 produced 2-nitro-1-phenylpropanol in the syn and the anti diastereoisomeric forms, with a considerable higher selectivity towards the former (66:34).

scholarly journals Carboxylated Chitosan Nanocrystals: Novel Synthetic Route and Application as Superior Support for Gold-Catalyzed Reactions

2020 ◽  
Author(s):  
Tony Jin ◽  
Davis Kurdyla ◽  
Sabahudin Hrapovic ◽  
Alfred Leung ◽  
Sophie Régnier ◽  
...  
Keyword(s):  
Imaging Techniques ◽  
Coupling Reaction ◽  
Primary Alcohols ◽  
X Ray Diffraction ◽  
Catalytic Activities ◽  
Glycosidic Bonds ◽  
Carboxylate Groups ◽  
Transmission Electron ◽  
Nitrophenol Reduction ◽  
Catalyzed Reactions

<p>Chitin nanocrystals (ChNCs) were prepared by partial cleavage of glycosidic bonds in chitin with concurrent oxidation of chitin C6 primary alcohols to produce carboxylate groups on the surface of the ChNCs. Following alkaline deacetylation of the ChNCs in the presence of NaBH<sub>4</sub> to inhibit “end-peeling” afforded chitosan nanocrystals (ChsNCs) with a degree of deacetylation (DDA) >80%. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform Infrared (FTIR) spectroscopy were used to determine the morphology and composition of these carboxylated ChNCs and ChsNCs. Subsequently, two methods were used to deposit Au onto the nanocrystals, and the catalytic activities of the resulting biomass-based nanocatalysts were tested for the 4-nitrophenol reduction and the aldehyde-amine-alkyne (A<sup>3</sup>) coupling reaction. In particular, Au nanoparticles over ChsNCs featured the highest turnover frequency value for the 4-nitrophenol reduction reported to date. Spectroscopic and imaging techniques confirmed the importance of controlling precisely the redox state of Au as it is being deposited to afford highly disperse active site on the bio-nano-support. </p>

syn and anti conformations in 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid and two related salts

2014 ◽  
Vol 70 (5) ◽  
pp. 493-497 ◽  
Author(s):  
Alexandr V. Yatsenko ◽  
Ksenia A. Paseshnichenko
Keyword(s):  
Density Functional Theory ◽  
Benzoic Acid ◽  
Density Functional ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Octahedral Environment ◽  
Carboxylate Groups ◽  
Distorted Octahedral ◽  
Benzene Rings

The crystal structures of 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoic acid, C13H9N3O5, (I), ammonium 2-hydroxy-5-[(E)-phenyldiazenyl]benzoate, NH4 +·C13H9N2O3 −, (II), and sodium 2-hydroxy-5-[(E)-(4-nitrophenyl)diazenyl]benzoate trihydrate, Na+·C13H8N3O5 −·3H2O, (III), have been determined using single-crystal X-ray diffraction. In (I) and (III), the phenyldiazenyl and carboxylic acid/carboxylate groups are in an anti orientation with respect to each other, which is in accord with the results of density functional theory (DFT) calculations, whereas in (II), the anion adopts a syn conformation. In (I), molecules form slanted stacks along the [100] direction. In (II), anions form bilayers parallel to (010), the inner part of the bilayers being formed by the benzene rings, with the –OH and –COO− substituents on the bilayer surface. The NH4 + cations in (II) are located between the bilayers and are engaged in numerous N—H...O hydrogen bonds. In (III), anions form layers parallel to (001). Both Na+ cations have a distorted octahedral environment, with four octahedra edge-shared by bridging water O atoms, forming [Na4(H2O)12]4+ units.

scholarly journals Carboxylated Chitosan Nanocrystals: Novel Synthetic Route and Application as Superior Support for Gold-Catalyzed Reactions

2020 ◽  
Author(s):  
Tony Jin ◽  
Davis Kurdyla ◽  
Sabahudin Hrapovic ◽  
Alfred Leung ◽  
Sophie Régnier ◽  
...  
Keyword(s):  
Imaging Techniques ◽  
Coupling Reaction ◽  
Primary Alcohols ◽  
X Ray Diffraction ◽  
Catalytic Activities ◽  
Glycosidic Bonds ◽  
Carboxylate Groups ◽  
Transmission Electron ◽  
Nitrophenol Reduction ◽  
Catalyzed Reactions

<p>Chitin nanocrystals (ChNCs) were prepared by partial cleavage of glycosidic bonds in chitin with concurrent oxidation of chitin C6 primary alcohols to produce carboxylate groups on the surface of the ChNCs. Following alkaline deacetylation of the ChNCs in the presence of NaBH<sub>4</sub> to inhibit “end-peeling” afforded chitosan nanocrystals (ChsNCs) with a degree of deacetylation (DDA) >80%. Transmission electron microscopy (TEM), X-ray diffraction (XRD) and Fourier-transform Infrared (FTIR) spectroscopy were used to determine the morphology and composition of these carboxylated ChNCs and ChsNCs. Subsequently, two methods were used to deposit Au onto the nanocrystals, and the catalytic activities of the resulting biomass-based nanocatalysts were tested for the 4-nitrophenol reduction and the aldehyde-amine-alkyne (A<sup>3</sup>) coupling reaction. In particular, Au nanoparticles over ChsNCs featured the highest turnover frequency value for the 4-nitrophenol reduction reported to date. Spectroscopic and imaging techniques confirmed the importance of controlling precisely the redox state of Au as it is being deposited to afford highly disperse active site on the bio-nano-support. </p>

scholarly journals Exo⇔Endo Isomerism, MEP/DFT, XRD/HSA-Interactions of 2,5-Dimethoxybenzaldehyde: Thermal, 1BNA-Docking, Optical, and TD-DFT Studies

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5970
Author(s):  
Nabil Al-Zaqri ◽  
Mohammed Suleiman ◽  
Anas Al-Ali ◽  
Khaled Alkanad ◽  
Karthik Kumara ◽  
...  
Keyword(s):  
Density Functional ◽  
Energy Gap ◽  
Structural Parameters ◽  
Population Analysis ◽  
Xrd Analysis ◽  
X Ray Diffraction ◽  
Optical Energy Gap ◽  
Functional Theory ◽  
Reactivity Descriptors ◽  
Td Dft

The exo⇔endo isomerization of 2,5-dimethoxybenzaldehyde was theoretically studied by density functional theory (DFT) to examine its favored conformers via sp2–sp2 single rotation. Both isomers were docked against 1BNA DNA to elucidate their binding ability, and the DFT-computed structural parameters results were matched with the X-ray diffraction (XRD) crystallographic parameters. XRD analysis showed that the exo-isomer was structurally favored and was also considered as the kinetically preferred isomer, while several hydrogen-bonding interactions detected in the crystal lattice by XRD were in good agreement with the Hirshfeld surface analysis calculations. The molecular electrostatic potential, Mulliken and natural population analysis charges, frontier molecular orbitals (HOMO/LUMO), and global reactivity descriptors quantum parameters were also determined at the B3LYP/6-311G(d,p) level of theory. The computed electronic calculations, i.e., TD-SCF/DFT, B3LYP-IR, NMR-DB, and GIAO-NMR, were compared to the experimental UV–Vis., optical energy gap, FTIR, and 1H-NMR, respectively. The thermal behavior of 2,5-dimethoxybenzaldehyde was also evaluated in an open atmosphere by a thermogravimetric–derivative thermogravimetric analysis, indicating its stability up to 95 °C.

Site preference and atomic ordering in the ternary Rh5Ga2As: first-principles calculations

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Nilanjan Roy ◽  
Sucharita Giri ◽  
Harshit ◽  
Partha P. Jana
Keyword(s):  
Total Energy ◽  
First Principles ◽  
Density Functional ◽  
Structure Type ◽  
Site Preference ◽  
X Ray Diffraction ◽  
Atomic Ordering ◽  
Functional Theory ◽  
The Stability ◽  
Bonding Characteristics

Abstract The site preference and atomic ordering of the ternary Rh5Ga2As have been investigated using first-principles density functional theory (DFT). An interesting atomic ordering of two neighboring elements Ga and As reported in the structure of Rh5Ga2As by X-ray diffraction data only is confirmed by first-principles total-energy calculations. The previously reported experimental model with Ga/As ordering is indeed the most stable in the structure of Rh5Ga2As. The calculation detected that there is an obvious trend concerning the influence of the heteroatomic Rh–Ga/As contacts on the calculated total energy. Interestingly, the orderly distribution of As and Ga that is found in the binary GaAs (Zinc-blende structure type), retained to ternary Rh5Ga2As. The density of states (DOS) and Crystal Orbital Hamiltonian Population (COHP) are calculated to enlighten the stability and bonding characteristics in the structure of Rh5Ga2As. The bonding analysis also confirms that Rh–Ga/As short contacts are the major driving force towards the overall stability of the compound.

scholarly journals Measuring the structure and equation of state of polyethylene terephthalate at megabar pressures

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
J. Lütgert ◽  
J. Vorberger ◽  
N. J. Hartley ◽  
K. Voigt ◽  
M. Rödel ◽  
...  
Keyword(s):  
Equation Of State ◽  
Polyethylene Terephthalate ◽  
Density Functional ◽  
Equations Of State ◽  
Md Simulations ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
Shock Hugoniot ◽  
Highly Correlated

AbstractWe present structure and equation of state (EOS) measurements of biaxially orientated polyethylene terephthalate (PET, $$({\hbox {C}}_{10} {\hbox {H}}_8 {\hbox {O}}_4)_n$$ ( C 10 H 8 O 4 ) n , also called mylar) shock-compressed to ($$155 \pm 20$$ 155 ± 20 ) GPa and ($$6000 \pm 1000$$ 6000 ± 1000 ) K using in situ X-ray diffraction, Doppler velocimetry, and optical pyrometry. Comparing to density functional theory molecular dynamics (DFT-MD) simulations, we find a highly correlated liquid at conditions differing from predictions by some equations of state tables, which underlines the influence of complex chemical interactions in this regime. EOS calculations from ab initio DFT-MD simulations and shock Hugoniot measurements of density, pressure and temperature confirm the discrepancy to these tables and present an experimentally benchmarked correction to the description of PET as an exemplary material to represent the mixture of light elements at planetary interior conditions.

A DFT study of spherands containing five anisyl groups — Highly preorganized to bind the alkali metal

2006 ◽  
Vol 84 (8) ◽  
pp. 1045-1049 ◽  
Author(s):  
Shabaan AK Elroby ◽  
Kyu Hwan Lee ◽  
Seung Joo Cho ◽  
Alan Hinchliffe
Keyword(s):  
Density Functional Theory ◽  
Binding Energy ◽  
Density Functional ◽  
Ionic Radius ◽  
Binding Energies ◽  
Cavity Size ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Good Agreement

Although anisyl units are basically poor ligands for metal ions, the rigid placements of their oxygens during synthesis rather than during complexation are undoubtedly responsible for the enhanced binding and selectivity of the spherand. We used standard B3LYP/6-31G** (5d) density functional theory (DFT) to investigate the complexation between spherands containing five anisyl groups, with CH2–O–CH2 (2) and CH2–S–CH2 (3) units in an 18-membered macrocyclic ring, and the cationic guests (Li+, Na+, and K+). Our geometric structure results for spherands 1, 2, and 3 are in good agreement with the previously reported X-ray diffraction data. The absolute values of the binding energy of all the spherands are inversely proportional to the ionic radius of the guests. The results, taken as a whole, show that replacement of one anisyl group by CH2–O–CH2 (2) and CH2–S–CH2 (3) makes the cavity bigger and less preorganized. In addition, both the binding and specificity decrease for small ions. The spherands 2 and 3 appear beautifully preorganized to bind all guests, so it is not surprising that their binding energies are close to the parent spherand 1. Interestingly, there is a clear linear relation between the radius of the cavity and the binding energy (R2 = 0.999).Key words: spherands, preorganization, density functional theory, binding energy, cavity size.

On tungstates of divalent cations (III) – Pb5O2[WO6]

2020 ◽  
Vol 235 (8-9) ◽  
pp. 311-317
Author(s):  
Stephan G. Jantz ◽  
Florian Pielnhofer ◽  
Henning A. Höppe
Keyword(s):  
Crystal Structure ◽  
Thermal Analysis ◽  
Quantum Chemical ◽  
Density Functional ◽  
Divalent Cations ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
First Results ◽  
Electrostatic Calculations

Abstract${\text{Pb}}_{5}{\text{O}}_{2}\left[{\text{WO}}_{6}\right]$ was discovered as a frequently observed side phase during our investigation on lead tungstates. Its crystal structure was solved by single-crystal X-ray diffraction ($P{2}_{1}/n$, $a=7.4379\left(2\right)$ Å, $b=12.1115\left(4\right)$ Å, $c=10.6171\left(3\right)$ Å, $\beta =90.6847\left(8\right)$°, $Z=4$, ${R}_{\text{int}}=0.038$, ${R}_{1}=0.020$, $\omega {R}_{2}=0.029$, 4188 data, 128 param.) and is isotypic with ${\text{Pb}}_{5}{\text{O}}_{2}\left[{\text{Te}}_{6}\right]$. ${\text{Pb}}_{5}{\text{O}}_{2}\left[{\text{WO}}_{6}\right]$ comprises a layered structure built up by non-condensed [WO6]${}^{6-}$ octahedra and ${\left[{\text{O}}_{4}{\text{Pb}}_{10}\right]}^{12+}$ oligomers. The compound was characterised by spectroscopic measurements (Infrared (IR), Raman and Ultraviolet–visible (UV/Vis) spectra) as well as quantum chemical and electrostatic calculations (density functional theory (DFT), MAPLE) yielding a band gap of 2.9 eV fitting well with the optical one of 2.8 eV. An estimation of the refractive index based on the Gladstone-Dale relationship yielded $n\approx 2.31$. Furthermore first results of the thermal analysis are presented.

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