Search results for "Theoretical Chemistry"
showing 10 items of 8456 documents
NMR Spectroscopic and quantum chemical characterization of the (E)- and (Z)- isomers of the penta-1,3-dienyl-2-cation
2003
Dilute solutions of the (E )− and (Z )− isomers of pent-1,3-dienyl-2-cations (1) were obtained from reaction of 4-chloro-1,2-pentadiene (2) with SbF5 in SO2ClF/SO2F2 at −135 °C using high-vacuum co-condensation techniques. The experimental NMR spectra of the mixture of the two isomers were compared with quantum chemical 13C NMR chemical shift calculations at HF-SCF, MP2, CCSD and CCSD(T) levels using MP2/tzp geometries. Quantum chemical shift calculations were performed with a tzp basis (9s5p1d/5s3p1d) for carbon and a dz basis (4s/2s) for hydrogen using gauge-including atomic orbitals (GIAOs). The HF-SCF calculations deviate significantly for the positively charged carbon atoms of the ally…
Reactivity of Distibanes toward Trialkylalanes and -gallanes: Syntheses and X-ray Structures of Bisadducts and Heterocycles
2001
Reactions between distibanes of the type Sb2R4 and trialkylalanes and -gallanes R‘3M in 1:2 stoichiometry yield eight bisadducts of the type [Sb2R4][MR‘3]2 (R = Me, R‘ = t-Bu, M = Al 1, Ga 2; R = Et, M = Al, R‘ = Me 3, Et 4, t-Bu 5; M = Ga, R‘ = Me 6, Et 7, t-Bu 8), which were characterized by multinuclear NMR studies and elemental analysis. In addition, 1, 2, 5, and 8 are the first structurally characterized neutral main group Lewis acid−distibane bisadducts. 1−8 are unstable in solution toward the formation of heterocycles of the type [R2SbMR‘2]x. [Me2SbGa(t-Bu)2]3 (9) and [Et2SbGa(t-Bu)2]2 (10) have been isolated and their solid state structures determined by single-crystal X-ray diffrac…
Crystal structures, infrared-spectra, and thermal behavior of calcium hydrogenselenite monohydrate, Ca(HSeO3)2 · H2O, and dicalcium diselenite bis(hy…
1986
Abstract Calcium hydrogenselenite monohydrate and dicalcium diselenite bis(hydrogenselenite) were synthesized and their crystal structures determined. Crystal data for Ca(HSeO3)2 · H2O: a = 6.911(2), b = 7.369(2), c = 6.739(2) A, α = 90.51(3)°, β = 90.93(3)°, γ = 107.46(2)°, V = 327.3(2) A3, space group P 1 (No. 2), dcalcd = 3.19 M gm−3, Z = 2, and R = 0.036 for 1503 reflections. Data for Ca2(HSeO3)2(Se2O5): a = 14.719(4), b = 7.059(2), c = 11.793(2) A, β = 117.96(2)°, V = 1082.3(4) A3, space group C2 c (No. 15), dcalcd = 3.52 Mg m−3, Z = 4, and R = 0.047 for 1251 reflections. Both structures form a three-dimensional network. The coordination polyhedron around calcium is a monocapped trigon…
Outer and inner coordination sphere chemistry of polyazacyclophane platinum(II) complexes. Crystal structure of [PtBr4]2(H4L1) · H2O (L1 = 2,6,9,13-t…
1997
Abstract The interaction of PtCl42− with the new azaparacyclophane 2,5,8,11-tetraaza[12]paracyclophane (L2) has been studied by 1H, 13C and 195Pt NMR spectroscopy. Three different complexes are detected as a function of pH, all of them presenting cis-arrangement of nitrogen donors and chloride anions. In the first one, formed at acidic pH, the central nitrogen atoms of the macrocyclic are coordinating to Pt(II) while the benzylic nitrogens remain protonated. Deprotonation of these nitrogens brings about a reorganisation of the complex, and the platinum is then coordinated by one benzylic nitrogen and the consecutive nitrogen in the macrocycle. This process can be monitored by NMR. Finally, …
High resolution study of the 3ν1 band of SO2
2009
Abstract The second overtone band 3 ν 1 of sulfur dioxide has been studied for the first time with high resolution rotation-vibration spectroscopy. About 3000 transitions involving about 900 upper state energy levels with J max. = 66 and K a max. = 24 have been assigned to the 3 ν 1 band. In the analysis, an effective Hamiltonian taking into account accidental interactions between the vibrational states (3 0 0), (2 2 0), and (0 4 1) was used. The Watson operator in A -reduction and I r representation was used in the diagonal blocks of the Hamiltonian. As the result of analysis a set of parameters reproducing the initial experimental data with the rms = 0.00028 cm −1 was obtained.
1D coordination polymer based on copper(II)-containing tetrameric 1,2,3-triazole ligand from click chemistry: Magnetic and catalytic properties
2019
Abstract A novel tetrameric tetra[O-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)]-pentaerythritol (TBTP) has been synthesized using click chemistry strategy. TBTP was characterized and used as ligand to form new Cu(II) complexes, forming 1-D coordination polymers. Two square planar complexes were characterized by single-crystal X-ray diffraction, presenting formula [Cu(TBTP)][Cu(NO3)4] (1) and [Cu(TBTP)](NO3)2 (2). In both structures, a cationic 1-D coordination polymer (CP) has been formed. The CP contain a 1:1 Cu(II)/TBTP ratio with four neutral triazole groups coordinating the Cu(II) center, forming a Cu N bonds ranging 1.988(2)–2.001(2) A. The study of the magnetic properties of compounds 1…
EFFECT OF SHAPE ON POTATO AND CAULIFLOWER SHRINKAGE DURING DRYING
2000
ABSTRACT Shrinkage of potato cubes, parallelepipeds and cylinders was addressed during drying. A basic methodology by using image analysis was set-up in order to measure and monitor geometrical changes along the drying process. Both measurements by image analysis and directly with a calliper were carried out. Results from both methods showed a good agreement with no bias. Particle shape was found to influence shrinkage in a different way according to the axis. In fact the larger dimension shrinks less than the shorter one. This could be linked to the influence of the core drying in shrinkage. Experiments were also carried out for cauliflower stems. The difference in shrinkage between direct…
On a topological interpretation of electronic and vibrational molecular energies
1998
Abstract A relationship between Randic's connectivity index and various quantum mechanical parameters derived from the Huckel Molecular Orbital (HMO) approach is demonstrated. When applied to conjugated hydrocarbons, this index represents the measure of the global π electron molecular energy and, therefore, of the resonance energy. Moreover, the development of the procedure, allows the introduction of a new definition of the bond order which, in turn, makes possible a better prediction not only for bond lengths of naphtalene but also for the resonance integral and conjugation energy for butadiene. Also, a corrected value for the Randic index is deduced, which allows for the reduction of the…
Unexpected magnetic topology in the heterobimetallic [ReIVBr4(μ-ox)CuII(bpy)2] compound
2011
Abstract A novel oxalato-bridged rhenium(IV)-copper(II) compound, namely [ReIVBr4(μ-ox)CuII(bpy)2] (1), has been obtained by reacting (PPh4)2[ReBr4(ox)] with Cu(CF3SO3)2 and 2,2′-bpy in CH3CN, and its crystal structure determined by single-crystal X-ray diffraction. Intermolecular Br⋯Br interactions and nonbonding Cu⋯Br type contacts between the heterobimetallic dinuclear units lead to a two-dimensional supramolecular structure. Compound 1 behaves magnetically as a [ReIVCuII]2 tetranuclear species with weak antiferromagnetic interactions through the oxalato bridge and intermolecular Br⋯Br contacts.
Theoretical electronic spectra of 2-aminopurine in vapor and in water
2006
The accurate quantum chemical CASSCF and CASPT2 methods combined with a Monte Carlo procedure to mimic solvation effects have been used in the calculation of the spectroscopic properties of two tautomers of 2-aminopurine (2AP). Absorption and emission spectra have been simulated both in vacuum and in aqueous environment. State and transition energies and properties have been obtained with high accuracy, leading to the assignment of the most important spectroscopic features. The lowest-lying 1 (,*) ( 1 La) state has been determined as responsible for the first band in the absorption spectrum and also for the strong fluorescence observed for the system in water. The combined approach used in …