Ionization and appearance potentials in organic chemistry. II—Appearance potentials and enthalpy differences for the stereoisomers of methylbicyclo[4.4.0]decanes

The ionization potentials for the stereoisomers of trans-fused 2- and 3-methylbicyclo[4.4.0]decanes and the appearance potentials for the ions at m/e 137 [M–CH₃]⁺, 109, 96, 95 and 82 were measured by the electron impact method. The ionization potentials and appearance potentials of the [M–CH₃]⁺ ions appeared to be equal for each of the epimers. Appearance potentials of the other ions were always lower for the less stable epimer. No quantitative correlation was observed between the difference in the appearance potentials for any ions and the differences in enthalpies of the ground states.     

Vibrational spectra and conformations of 2- and 3-methylbicyclo[4.4.0]decanes

The conformations and heats of formation of all trans(T)- and cis(C)-2- and 3-methyl-substituted T- and Cbicyclo[4.4.0]decanes (BD) were calculated by the MM2 method of molecular mechanics. It was shown that the conformationally mobile T-2-Me-CBD and T-3-Me-CBD can exist in normal conditions as an inseparable mixture of conformers with a different equatorial or axial orientation of the Me groups. The Raman scattering (RS) spectra of TBD and CBD were investigated. RS bands whose frequencies were sensitive to the type of ring linkage and orientation (but not the position) of the Me substituents were detected in the 700–300 cm^–1 region.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2089–2097, September, 1992.     

X-ray study of the molecular structure of α-mercury and α-platinummercury derivatives of l-menthyl phenylacetate

The molecular structures of the L-menthyl ester of S-α-bromomercuriphenyl-acetic acid, diastereomer II, [α]²⁰_D ?18°, and of the related L-menthyl ester of α-bromobis(triphenylphosphine)platinummeruriphenylacetic acid, VI, have been investigated by the X-ray method. Insertion of L₂Pt carbenoid appears to occur into the HgBr bond in II and two phosphine ligands in the product VI occupy cis positions in a planar square around the platinum atom. The HgPt distance is 2.50 Å; there is intermolecular HgBr coordination in II, the distance being 3.23 Å.     

Structure,stability, and electronic and NMR properties of various oxo- and nitrido-derivatives of [L(Salen)Mn(III)]+, where L = none and imidazole. A density functional study

Structure, stability, and electronic and NMR properties of [(Salen)Mn(III)](+)-derived intermediates/reactants in the epoxidation/amination of unfunctionalized olefins, namely [(Salen)Mn(V)O](+) (1-oxo), [(Salen)Mn(IV)O] (2-oxo), and [(Salen)Mn(V)N] (3), have been studied with the B3LYP density functional method. It has been shown that the (1)A, (3)A, and (5)A states of cationic 1-oxo species are virtually degenerate, while for the neutral 2-oxo species the ground (4)A state lies 6.4 kcal/mol lower than (2)A. In the nitrido species 3, the (1)A state has been shown to be the ground state in agreement with experiment. We have investigated isomerization of 1-oxo and 2-oxo species into unusual [(OSalen)Mn(III)](+) (1-N-oxo and 1-peroxo) and [(OSalen)Mn(II)] (2-N-oxo and 2-peroxo) species, respectively. For cationic species 1, the 1-N-oxo isomers are more stable (by 10-12 kcal/mol) than the 1-oxo isomer and are separated from the latter by 21-22 kcal/mol barriers. On the other hand, 1-peroxo isomers are calculated to be 14-16 kcal/mol higher than the 1-oxo isomer. For neutral species 2, however, both 2-N-oxo and 2-peroxo isomers lie significantly higher in energy than the 2-oxo isomer. It has been shown that coordination of axial imidazole ligand alters relative energies of spin states for 1- and 2-oxo species, destabilizing low-spin states. For singlet states of H(2)Salen, 1-oxo, and 3, we have calculated (1)H, (13)C, (15)N, and (17)O NMR chemical shifts using the gauge-independent-atomic orbital (GIAO) approach.     

A comparative study of various computational approaches in calculating the structure of pyridoxal 5'-phosphate (PLP)-dependent beta-lyase protein. The importance of protein environment

Various computational approaches, using molecular mechanics (Amber), semiempirical (AM1), density functional (B3LYP), and various ONIOM methods, have been comparatively investigated for the structure of Escherichia coli NifS CsdB protein. The structure of the entire monomer containing 407 amino acid residues and 579 surrounding water molecules has been optimized. The full geometry optimization in the "active site-only" approach (including only active site atoms) has been found to give the largest root-mean-square (RMS) deviation from the X-ray structure; a much better agreement has been achieved by keeping the atoms leading to the backbones of some amino acids frozen in their positions in the X-ray structure. The best agreement has been attained by including the surrounding protein in the calculations using the two-layer ONIOM (B3LYP:Amber) approach. The results presented in this study conclusively demonstrate the importance of the protein/active-site interaction on the active-site structure of the enzyme. The present theoretical study represents the largest system studied at the ONIOM level to date, containing 7992 atoms, including 84 atoms in the QM region and rest in the MM region.     

A comparative investigation of the fatty acid compositions of the seeds of a number of lines of a genetic collection of Gossypium hirsutum

A comparative analysis has been made of the amounts of lipids and their fatty-acid compositions in the seeds of the lines of agenetic collection of cotton plants of the speciesGossypium hirsutum and their hybrids and the variety Tashkent-1. The results obtained on the fatty-acid compositions of some hybrids make it possible to recommend the use of individual lines of cotton plants as donors for improving the food-value indices of cottonseed oil.Institute of Chemsitry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–176, March–April, 1991.     

Theoretical investigation of the structure and stability of salt molecules LiOF,LiOCl, LiSF,LiSCl and ion-molecular complexes Li+·F2, Li+·FCl,and Li+·Cl2

Institute of New Chemical Problems, Russian Academy of Sciences, Chernogolovka. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 1, pp. 3–9, January–February, 1992.     

Computational study of the aminolysis of esters. The reaction of methylformate with ammonia

The aminolysis of esters is a basic organic reaction considered as a model for the interaction of carbonyl group with nucleophiles. In the present computational study the different possible mechanistic pathways of the reaction are reinvestigated by applying higher level electronic structure theory, examining the general base catalysis by the nucleophile, and a more comprehensive study the solvent effect. Both the ab initio QCISD/6-31(d,p) method and density functional theory at the B3LYP/6-31G(d) level were employed to calculate the reaction pathways for the simplest model aminolysis reaction between methylformate and ammonia. Solvent effects were assessed by the PCM method. The results show that in the case of noncatalyzed aminolysis the addition/elimination stepwise mechanism involving two transition states and the concerted mechanism have very similar activation energies. However, in the case of catalyzed aminolysis by a second ammonia molecule the stepwise mechanism has a distinctly lower activation energy. All transition states in the catalyzed aminolysis are 10-17 kcal/mol lower than those for the uncatalyzed process.