Evidence that there is a future for semiempirical molecular orbital calculations

The frequency of use and discussion of semiempirical and ab initio software is traced with bibliometric data from the Current Journals of the American Chemistry Society (JCACS) database, which has complete papers published in 19 journals in various fields of chemistry. Not only is the use of all types of computational chemistry software increasing apace, but also the number of papers mentioning semiempirical programs as a percentage of all papers mentioning quantum chemistry programs is growing. This percentage referring to semiempirical molecular orbital software grew from 29% in 1989 to 34% in 1993.     

Structural studies of immobilized ethylenediamine as a preconcentrating agent for molybdate and tungstate

The structure of the complex formed between molybdate and the diamine functional group of N-β-aminoethyl-γ-aminopropylsilane (Dow Corning 2-6020) immobilized on a silica substrate is determined and compared with the analogous complex precipitated from solution. Infrared spectroscopy and photoacoustic spectroscopy were applied to establish the nature of the complex. The precipitate formed with ethylenediamine contains a polymeric molybdate species, whereas the molybdate retained by the immobilized ethylenediamine group is monomeric. Trace levels of tungstate and molybdate can be extracted from aqueous concentrated sodium chloride solutions on a column packed with controlled-pore glass beads treated with Z-6020.     

A quantum-chemical study of the structure, vibrations and SiH bond properties of disilylamine, NH(SiH3)2

Quantum-chemical calculations at HF, MP2 and B3LYP levels with 6-31G* and 6-311G** basis sets are reported for disilylamine, NH(SiH3)2. The equilibrium structure is found to vary with both level and basis set, all but one of the structures exhibiting a small lack of planarity of the HNSi2 system. The barrier to inversion, however, is found to be very low, at most 38 cm(-1). Vibration frequencies and intensities are calculated. The frequencies are scaled, where possible, either using updated infrared data or with the aid of factors transferred from N(CH3)(SiH3)2. Unobserved frequencies due to the v(s)NSi2, deltaNSi2 and delta(perpendicular)NH modes are predicted near 610, 210 and 360 cm(-1), respectively. The lower silyl torsion lies below 40 cm(-1). The appearance of a single broad vSiH band in gas-phase samples of both NH(SiH3)2 and NH(SiH3)(SiD3) is suggestive of signal averaging due to internal rotation. The frequencies v(is)SiH, infrared intensities and Raman scattering activities of the bands due to an isolated SiH bond in an otherwise deuterated species are calculated and correlated with the torsional angle of this bond and with the Mulliken charge on the hydrogen atom. The strength of the bond is a minimum, and the infrared intensity and Raman scattering activity are maxima, when the bond direction is roughly orthogonal to the skeletal plane. A major part of the frequency and intensity variations is attributed to n(p)(N)-sigma*(Si-H)) hyperconjugation which, NBO calculations show, reaches a maximum for this conformation. However, systematic smaller variations are found for SiH bonds lying in the skeletal plane, which reflect the proximity of the other silyl group and only partly correlate with Mulliken charge. vSiH-vSiH interaction force constants, f', are calculated for pairs of SiH bonds in different silyl groups and compared with the corresponding dipole-dipole potential energy, the latter calculated using a classical treatment of the interaction between point dipoles arising from delta mu/delta r for the SiH bonds involved. The gradient of the correlation is very close to that expected from the theory, but a negative intercept indicates the presence of additional factors.     

Infrared investigation of the reactions of rhodiumcarbonyl halides and carbon monoxide at elevated pressures

Infrared spectral results at elevated carbon monoxide pressures suggest that rhodiumdicarbonyl halides and carbon monoxide exist in an equilibrium with the corresponding rhodiumtricarbonyl halides.     

On the rate and activation energy of the Br + Br2 ataom-exchange reaction

The Br + Br₂ atom-exchange reaction has been studied using quasiclassical trajectories and a semi-empirical potential-energy surface with shallow, long-range wells. The computed reaction rate coefficient is in good agreement with experiment. The computed reaction activation energy is ? 1 kcal/mole.     

Stereoregular polymerization of 1-vinylnaphthalene, 2-vinylnaphthalene,and 4-vinylbiphenyl

1-Vinylnaphthalene, 2-vinylnaphthalene, 4-vinylbiphenyl, and styrene were polymerized with Et₃Al–TiCl₄, Et₂AlCl–TiCl₃, and Et₃Al–TiCl₃ catalyst systems. The latter catalyst system gave polymers in 75–95% conversion which were at least 90% isotactic. Extraction with 2-butanone (MEK) separated the atactic from the isotactic fractions. The polymers were characterized by infrared and nuclear magnetic resonance spectroscopy.     

Advantages of deuterium modification of nitroxide spin labels for biological epr studies

The spin label, perdeuterio-N-(1-oxy 1-2,2,6,6-tetramenthyl-4-piperidinyl)maleimide (DMSL) was synthesized and its EPR and saturation transfer EPR spectra were compared to those of the hydrogen analogue, HMSL- The labels were studied as freely tumbling entities and also bound to bovine serum albumin (BSA). Significant gains in spectral resolution and detectability were observed for DMSL relative to HMSL.     

Synthesis of 1,4,5,6‐tetrahydropyrazolo[3,4‐d]pyrido[3,2‐b]azepine

The synthesis of 7,8‐dihydro‐5(6H)‐quinolinone ( 3 ) from commercially available 3‐amino‐2‐cyclohexen‐1‐one ( 1 ) and 3‐(dimethylamino)acrolein ( 4 ) in 23% yield avoids the preparation of propynal ( 2 ). Conversion of 5‐(4‐methylphenylsulfonyl)‐6,7,8,9‐tetrahydro‐5H‐pyrido[3,2‐b]azepine ( 12 ) to 6‐(4‐methylphenylsulfonyl)‐1,4,5,6‐tetrahydropyrazolo[3,4‐d]pyrido[3,2‐b]azepine ( 24 ) is described. Removal of the N‐(4‐methylphenylsulfonyl) group with 40% sulfuric acid in acetic acid gave the tricyclic azepine 26. Application of a similar series of reactions to 5‐(4‐nitrobenzoyl)‐6,7,8,9‐tetrahydro‐5H‐pyrido[3,2‐b]‐azepine ( 13 ) afforded 6‐(4‐nitrobenzoyl)‐1,4,5,6‐tetrahydropyrazolo[3,4‐d]pyrido[3,2‐b]azepine ( 25 ).     

Time‐Resolved Phase Transitions of the Nanocrystalline Cubic to Submicron Monoclinic Phase in Mn2O3‐ZrO2

The nanocrystalline cubic phase of zirconia was found to be thermally stabilized by the addition of 3 to 40 mol % manganese. The nanocrystalline cubic, tetragonal and monoclinic phases of zirconia stabilized with manganese (III)oxide (Mn‐Stabilized Zirconia) were prepared by thermal decomposition of carbonate and hydroxide precursors. Both the crystallization and isothermal phase transitions associated with Mn‐SZ were studied using high temperature x‐ray diffraction and x‐ray diffraction of quenched samples. Cubic Mn‐SZ initially crystallized and progressively transformed to tetragonal, and monoclinic structures above 700°C. The nanocrystalline cubic Mn‐SZ containing 25 mol % Mn was found to have the greatest thermal stability, retaining its cubic form at temperatures as high as 800°C for periods up to 25 hours. Higher than 40 mol %, cubic Mn₂O₃ was found to coexist with cubic Mn‐SZ. The crystallite sizes observed for the cubic, tetragonal and monoclinic Mn‐SZ phases ranged from 50 to 137, 130 to 220, and 195 to 450 Å respectively, indicating, for ZrO₂, that particle size was a primary factor in determining its polymorphs. The classical Avrami equation for nucleation and growth was applied to the observed phase transformations.     

The antiestrogen [2‐(4‐benzyl­phenoxy)­ethyl]­diethyl­ammonium chloride

The crystal structure of the title compound, C₁₉H₂₆NO⁺·Cl^? (common name: N,N‐diethyl‐2‐[(4‐phenyl­methyl)phenoxy]‐ethan­amine hydro­chloride), contains one mol­ecule in the asymmetric unit. The planes through the two phenyl rings are roughly perpendicular. Protonation occurs at the N atom, to which the Cl^? ion is linked via an N—H?Cl hydrogen bond. The mol­ecule adopts an eclipsed rather than extended conformation.