New Constituents from the Leaves of Date Palm (Phoenix dactylifera L.) of Saudi Origin.

The phytochemical analysis of the butanolic extract from the leaves of date palm of Saudi origin resulted in the isolation of three major constituents, oleanolic acid (1), vanillyl alcohol (2), and ß-sitosterol-3-O-ß-d-glucoside (3), which had not been isolated from this plant or previously reported. Together, compounds 1 and 2 account for 1.0% of the butanol extract, which represents 0.4% of the mass of the dried leaves. The isolation of other known compounds for this plant such as fatty acids, lutein, and sucrose was also achieved in this study. The characterization and identification of the isolated compounds were conducted on the basis of Fourier-transform infrared spectroscopy (FTIR), 1H and 13C nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), and gas chromatography-mass spectrometry (GC-MS) analyses. The findings of the current study will definitely increase the knowledge about the contribution of the constituents of this plant to its well-known nutrition, corrosion inhibition, and antimicrobial properties.

Isolation of New Constituents from Whole Plant of Salsola imbricata Forssk. of Saudi Origin.

This work describes the first report of the known glycosidic constituents ß-sitosterol-3-O-ß-d-glucoside-6'-palmitate (1), ß-sitosterol-3-O-ß-d-glucoside (2), momor-cerebroside I (3), phytolacca cerebroside (4), 1,2-di-O-palmitoyl-3-O-(6-sulfoquinovopyranosyl)-glycerol (5), isorhamnetin-3-robinobioside (6), and isorhamnetin-3-rutinoside (7) from the plant Salsola imbricata Forssk. grown in the eastern region of Saudi Arabia. The structures of the isolated compounds were elucidated from extensive 1D and 2D nuclear magnetic resonance (NMR), gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), and chemical analyses. Compound 1 is reported for the first time from the Amaranthaceae family. In addition to the isolated and identified fatty alcohols, compounds 3, 4, 5, and 6 are also reported for the first time from the genus Salsola. The findings of this study suggest a contribution of the isolated compounds to the various biological activities reported for this plant.

Anticorrosion Properties of a Novel Hybrid Sol-Gel Coating on Aluminum 3003 Alloy.

In this study, a novel hybrid sol-gel coating on AA3003 substrate was developed and the effects of various waste material additives on the reinforcement of the sol-gel coating and the anticorrosion properties in the saline medium were investigated. Egg shell, crumb rubber, activated carbon obtained for pyrolysis of waste rubber tire, waste rubber tire, cement kiln dust, and ST100 additives were tested as reinforcement materials. The AFM characterization results of the coating formulations on AA3003 alloy revealed enhanced roughness values for the modified coatings as compared to the base coating. Similarly, no significant changes were detected in the Fourier transform infrared spectroscopy (FTIR) absorption peaks of the hybrid polymeric material upon loading it with the waste additives, while slight changes in the hydrophobic properties of the final modified coatings were observed as a result of the modification process. Electrochemical impedance spectroscopy (EIS) results revealed that the hybrid sol-gel coating had a promising potential for the protection of the AA3003 substrate against corrosion in the saline medium. However, the loaded additives negatively affected the corrosion resistance properties of the parent hybrid sol-gel coating. For instance, the egg shell additive had the least negative effect on the barrier properties, whereas the cured coating layer of the sample loaded with cement and clay additives showed some disintegration, inhomogeneity, and low barrier properties on the metal surface.

Regioselective Synthesis of Chromones via Cyclocarbonylative Sonogashira Coupling Catalyzed by Highly Active Bridged-Bis(N-Heterocyclic Carbene)Palladium(II) Complexes.

The one-pot regioselective and catalytic synthesis of bioactive chromones and flavones was achieved via phosphine-free cyclocarbonylative Sonogashira coupling reactions of 2-iodophenols with aryl alkynes, alkyl alkynes, and dialkynes. The reactions are catalyzed by new dibromidobis(NHC)palladium(II) complexes. The new bridged N,N'-substituted benzimidazolium salts (L1, L2, and L3) and their palladium complexes C1, C2, and C3 were designed, prepared, and fully characterized using different physical and spectroscopic techniques. The molecular structures of complexes C1 and C3 were determined by single-crystal X-ray diffraction analysis. They showed a distorted square planar geometry, where the Pd(II) ion is bonded to the carbon atoms of two cis NHC carbene ligands and two cis bromido anions. These complexes displayed a high catalytic activity in cyclocarbonylative Sonogashira coupling reactions with low catalyst loadings. The regioselectivity of these reactions was controlled by using diethylamine as the base and DMF as the solvent.

Soft Heteroleptic N-Heterocyclic Carbene Palladium(II) Species for Efficient Catalytic Routes to Alkynones via Carbonylative Sonogashira Coupling.

N,N'-Substituted di-isopropyl (NHC-1), benzyl-isopropyl (NHC-2), and adamantyl-isopropyl (NHC-3) benzimidazolium salts react with palladium(II) bromide in pyridine to afford the corresponding trans-dibromidopyridinepalladium(II) complexes Pd-C1, Pd-C2, and Pd-C3 in high yields. A distorted square planar geometry for Pd-C2 and Pd-C3 was confirmed by single-crystal X-ray diffraction. The palladium(II) complexes show a remarkably higher catalytic activity and selectivity, compared to the literature data, in carbonylative Sonogashira coupling reactions of aryl iodides and aryl diiodides with aryl alkynes, alkyl alkynes, and dialkynes. Excellent yields with as low as 0.03 mol % loading of the catalyst were obtained. In the series of benzimidazolium (NHC) precursors, the 1H NMR signals of the α hydrogen show a consistent probing of the N-substituent donor strength. The density functional theory (DFT) quantum mechanical descriptors of the frontier orbitals were calculated. A linear correlation of the calculated absolute softness of the complexes versus the calculated percent buried volume (%V bur) of their corresponding ligands was obtained. The catalytic activity experimental data are consistent with the hard soft acid base (HSAB)-predicted high affinity of the softest Pd-C3 complex for soft substrates, such as aryl iodides.

Ring inversion, structural stability and vibrational assignments of sulfolane c-C4H8SO2 and 3-sulfolene c-C4H6SO2.

The structural stability of sulfolane (tetrahydrothiophene1,1-dioxide) and 3-sulfolene (dihydrothiophene1,1-dioxide) was investigated by DFT-B3LYP and ab initio MP2 calculations with 6-311+G**) basis set. The calculated symmetric ring-puckering potential of 3-sulfolene at the B3LYP level is consistent with a flat minimum that corresponds to a planar ring but at the MP2 level with a double minimum with a low barrier of about 193 cal mol(-1) to ring planarity in reasonable agreement with experimental results. From the calculations at the two levels of theory sulfolane was predicted to exist predominantly in the twist conformation. The vibrational wavenumbers were calculated at the MP2/6-31G** level of theory and the potential energy distributions PED among the symmetry coordinates of the normal modes were computed for the low-energy structure of the molecules. Complete vibrational assignments were provided on the basis of the calculated PED values. The experimental infrared and Raman spectra of the two molecules were compared to the calculated ones.

Temperature dependence of the crystal lattice organization of coordination compounds involving nitronyl nitroxide radicals: a magnetic and structural investigation.

Four new mononuclear complexes of formula Cd(PN)(4)(NCS)(2) (A), Cd(PNN)(4)(N(3))(2) (B), Zn(PNN)(4)(N(3))(2) (C), and Zn(PNN)(2)(NCS)(2) (D), where PNN stands for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide and PN for 2-(4-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl, were synthesized and structurally and magnetically characterized. The X-ray structures of compounds B and C were also determined at 90 K. Compounds A[bond]C crystallize in the triclinic space group P 1 macro (No. 2), and D crystallizes in the monoclinic space group P2(1)/m (No. 11). A[bond]C adopt a centrosymmetric distorted octahedral geometry in which the metal ions are bonded to four radical ligands through the nitrogen atom of the pyridyl rings and the azido or thiocyanato ligands occupy the apical positions. Compound D adopts a distorted tetrahedral geometry in which the zinc ion is bonded to two radicals and two thiocyanato ligands. As suggested by their magnetic behavior, the low-temperature X-ray structures of B and C show that these compounds undergo a clear structural change with respect to the room-temperature structures. The experimental magnetic behaviors were perfectly reproduced by a dimer model for A[bond]C and an alternating chain model for D while the sudden breaks observed in the chi(M)T versus T curves for B and C were well accounted for by the high- and low-temperature X-ray structures. For all these complexes the crystal structures favor significant overlap between molecular magnetic orbitals leading to rather strong intermolecular antiferromagnetic interactions.

Metal-dependent ferro- versus antiferromagnetic interactions in molecular crystals of square Planar (M(II) imino-nitroxide radical) complexes (M = Pt, Pd).

The synthesis and structural, spectral, and magnetic characterizations of two new complexes of formula [Pt(IM(2)Py)Cl(2)] (A) and [Pd(IM(2)Py)Cl(2)] (B) are reported. IM(2)Py stands for the imino-nitroxide radical ligand 2-(ortho-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl. Their crystal structures were solved at room temperature and at 120 K revealing structural phase transitions from pseudo-orthorhombic to monoclinic systems for the two compounds which remain isostructural in the whole temperature range explored. Structural parameters for A: T = 293 K [120 K], monoclinic (P2(1)/n) [P2(1)/c], a = 7.906(2) [7.989(3)] A, b = 17.872(9) [10.168(4)] A, c = 10.357(3) [17.623(6)] A, beta = 90.732(13) degrees [95.940(2)] degrees, Z = 4 [4]. Structural parameters for B: T = 293 K [120 K], monoclinic (P2(1)/n) [P2(1)/c], a = 7.900(3) [7.9730(2)] A, b = 17.907(9) [10.1806(3)] A, c = 10.299(3) [17.7171(4)] A, beta = 90.524(14) degrees [95.747(2)] degrees, Z = 4 [4]. In both complexes, the metal coordination is essentially planar. The average Pt-N, Pt-Cl and Pd-N, Pd-Cl bond lengths are 1.996(6) [1.88], 2.295(2) [2.248(8)] A and 2.015(7) [2.029(8)], 2.287(3) [2.294(3)] A, respectively. The solid state structure is characterized by a pairlike molecular packing stacked in columns parallel to the a axis; this dimer character is reinforced at low temperature. Despite their structural similarity, the investigation of the magnetic properties revealed that dominant ferromagnetic interactions govern the behavior of the Pt derivative A, whereas antiferromagnetic interactions take place for the Pd compound B. A rationalization for this rather intriguing difference is proposed in light of the spin population deduced from density functional theory calculations. The electronic absorption spectra of A and B present structured absorption bands in the visible which are attributed to MLCT transitions. Both compounds are nonluminescent at room temperature. However, a weak emission is detected for A in butyronitrile glasses at 77 K, indicating that the MLCT excited state is strongly quenched at low temperature.