Molecular mechanics calculations of tin-bis (triphenylphosphine oxide) complexes

The capability of molecular mechanics for modeling the wide distribution of bond angles and bond lengths characteristic of coordination complexes was investigatecl. This was the preliminary step for future modeling of solvent extraction. Several tin-phosphine oxide COrnI)le:){es were selected as the test groUl) for t.he d,esired range of geometry they eX!libi ted as \-vell as the ligands they cOD.tained r Wllich were c\f interest in connection with solvation. A variety of adjustments were made to Allinger's M:M2 force·-field ill order to inl.prove its performance in the treatment of these systems. A set of u,nique force constants was introduced for' those terms representing the metal ligand bond lengths, bond angles, and, torsion angles. These were significantly smaller than trad.itionallY used. with organic compounds. The ~1orse poteIlt.ial energ'Y function was incorporated for the M-X l')ond lE~ngths and the cosine harmonic potential erlerg-y function was invoked for the MOP bond angle. These functions were found to accomodate the wide distribution of observed values better than the traditional harmonic approximations~ Crystal packing influences on the MOP angle were explored thr"ollgh ttle inclusion of the isolated molecule withil1 a shell cc)ntaini11g tl1e nearest neigl1'bors duri.rlg energy rninimization experiments~ This was found to further improve the fit of the MOP angle.

The crystal and molecular structure of bis (pyridoxamine) copper (II) dinitrate monohydrate

The crystal structure of Cu(PM)2(N03hoH20 (where PM is pyridoxamine, CSHI2N202) has been determined from three dimensional x-ray diffraction data. The crystals are triclinic, space group pI, a = 14.248 (2), b = 8.568 (1), c = 9.319 (1) 1, a = 94.08 (1), e = 89.73 (1), y~~ 99.18 (1)°, z = 2, jl(MoK) = 10.90 em-I, Po = 1.61 g/cm3 and Pc = 1.61 g/em3• The structure a was solved by Patterson techniques from data collected on a Picker 4-circle diffractometer to 26max = 45°. All atoms, including hydrogens, have been located. Anisotropic thermal parameters have been refined for all nonhydrogen atoms. For the 2390 independent reflections with F ? 3cr(F) , R = 0.0408. The results presented here provide the first detailed structural information of a metal complex with PM itself. The copper atoms are located on centres of symmetry and each is chela ted by two PM zwitterions through the amino groups and phenolate oxygen atoms. The zwitterionic form found in this structure involves the loss of a proton from the phenolate group and protonation of the pyridine ring nitrogen atoms. The two independent Cu(PM)2 moieties are symmetrically bridged by a single oxygen atom from one of the nitrate groups. The second nitrate group is not coordinated to the copper atoms but is central to an extensive hydrogen bonding network involving the water molecule and uncoordinated functional groups of PM.

The kinetics and mechanism of the thermal decomposition of bis diphenyl methyl and related peroxides in liquid phase /|nby C. Thankachan. -- 260 St. Catharines, Ont. : [s. n.],

Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

Bis-and tris (amidine) fluoroboron cations and related systems studies by Multinuclear NMR and fast atom bombardment mass spectometry

The formation and the isolation of fluoroboron salts, (D2BF2+)(PF6-), (DD'BF2+)(PF6-) and (D3BF2+)(PF6-)2, have been carried out. 1,8-Diazabicyclo [5,4.0]undec-7-ene (DBU) and 1,5-diazabicyclo[4,3,O]non-5-ene (DBN), extremely strong organic bases, were introduced into the fluoroboron cation systems and induced a complicated redistribution reaction in the D/BF3/BC13 systems. The result was the formation of all BFnCI4-n-, D.BFnCI3-n and fluoroboron cation species which were detected by 19p and 11B NMR spectrometry. The displacement reaction of CI- from these D.BFnCI3-n (n = 1 and 2) species by the second entering ligand is much faster than in other nitrogen donor containing systems which have been previously studied. Tetramethylguanidine, oxazolines and thiazolines can also produce similar reactions in D/BF3/BCI3 systems, but no significant BFnC4-n- species were observed. As well as influences of their basicity and their steric hindrance, N=C-R(X) (X = N, 0 or S) and N=C( X)2 (X = N or S) structures of ligands have significant effects on the fonnationof fluoroboron cations and the related NMR parameters. D3BF2+ and some D2BF2+ show the expected inertness, but (DBU)2BF2+ shows an interestingly high reactivity. (D2BF2+)(X-) formed from weak organic bases such as pyridine can react with stronger organic bases and form DD'BF2+ and D'2BF2+ in acetone or nitromethane. Fast atom bombardment mass spectrometry is doubly meaningful to this work. Firstly, FABMS can be directly applied to the complicated fluoroboron cation containing solution systems as an excellent complementary technique to multinuclear NMR. Secondly, the gas-phase ion substitution reaction of (D2BF2+)(PF6-) with the strong organic bases is successfully observed in a FABMS ion source when the B-N bond is not too strong in these cations.

Nuclear magnetic resonance studies of boron trihalide complexes of 1,1-BIS (dimethylamino) ethylene and related bases

Boron tribalide complexes of 1,1-bis(dimethylamino)ethylene (DME) , t etramethylurea (TMU), tetramethylguanidine (TMG) , and pentamethylguanidine (PMG) and also mixed boron t r ihalide adducts of DME have been investigated by 1H and 19F NMR spectroscopy. Both nitrogen and the C-Q-H carbon of DME are possible donor a toms to boron trihal ides but complexation has been found to occur only at carbon of DME. The initial adduct acts as a Bronsted acid and gives up a proton to free DME in solut ion. A side reaction in the DME-BF, system gives rise to trace amounts of a complex aSSigned as (DME)2BF2+. (DME)2BF2+ is produced in much larger quantities in t he DME-BF3-BC13 and DME-BF,-BBr, systems by reaction of free DME with DME:BF2X (X = Cl, Br). Restricted r otation about the C-N bonds of TMUlBC13 and n1U:BBr3 has been observed at low temperatures. This complements previous work in this system and confirms oxygen donation of TMU to boron trihalides . Restricted rotation at low temperatures also has been observed in DMEboron trihalide systems

Estudio del (2-(Bis-(N-acetilsulfanililimino) -4 Tiazolina

Tesis (Maestría en Ciencias con Especialidad en Química Orgánica) UANL

La asistencia legal al testigo y su situación procesal en la averiguación previa (Análisis del artículo 127 Bis del Código Federal de Procedimientos Penales)

Tesis ( Maestría en Ciencias Penales) U.A.N.L.

La inconstitucionalidad del artículo 21 Bis-8 de la Ley de Hacienda para los Municipios del Estado de Nuevo León

Tesis (Maestría en Derecho Fiscal ) U.A.N.L.

Molecular Networks Created by Charge-Assisted Hydrogen Bonds Between Bis(aminidinium) Cations and Carboxylates, Sulfonates, Phosphonates and Phosphates

L'objectif de cette étude est d'apprendre à créer de nouveaux matériaux moléculaires par design. À l'heure actuelle, il n'existe aucune méthode générale pour la prédiction des structures et des propriétés, mais des progrès importants ont été accomplis, en particulier dans la fabrication de matériaux moléculaires ordonnés tels que des cristaux. En ces matériaux, l'organisation peut être contrôlée efficacement par la stratégie de la tectonique moléculaire. Cette approche utilise des molécules appelées “tectons”, qui peuvent s’associer de manière dirigée par des interactions non covalentes prévisibles. De cette façon, la position de chaque molécule par rapport à ses voisins peut être programmée avec un degré élevé de fiabilité pour créer des cristaux et d'autres matériaux organisés avec des caractéristiques et des propriétés structurelles souhaitables. Le travail que nous allons décrire est axé sur l'utilisation de l'association des cations bis(aminidinium) avec des carboxylates, sulfonates, phosphonates et phosphates, afin de créer des réseaux moléculaires prévisibles. Ces réseaux promettent d'être particulièrement robuste, car ils sont maintenus ensemble par de multiples liaisons hydrogène assistées par des interactions électrostatiques.

Biochemical Effect of Dicarboxylic Acids on Oxalate Metabolism in Experimental Rats and Studies on Oxalate Degrading Bacteria

The current study is an attempt to find a means of lowering oxalate concentration in individuals susceptible to recurrent calcium oxalate stone disease.The formation of renal stone composed of calcium oxalate is a complex process that remains poorly understood and treatment of idiopathic recurrent stone formers is quite difficult and this area has attracted lots of research workers. The main objective of this work are to study the effect of certain mono and dicarboxylic acids on calcium oxalate crystal growth in vitro, isolation and characterization of oxalate degrading bacteria, study the biochemical effect of sodium glycollate and dicarboxylic acids on oxalate metabolism in experimental stone forming rats and To investigate the effect of dicarboxylic acids on oxalate metabolism in experimental hyperoxaluric rats. Oxalic acid is one of the most highly oxidized organic compound widely distributed in the diets of man and animals, and ingestion of plants that contain high concentration of oxalate may lead to intoxication. Excessive ingestion of dietary oxalate may lead to hyperoxaluria and calcium oxalate stone disease.The formation of calcium oxalate stone in the urine is dependent on the saturation level of both calcium and oxalate. Thus the management of one or both of these ions in individuals susceptible to urolithiasis appears to be important. The control of endogenous oxalate synthesis from its precursors in hyperoxaluric situation is likely to yield beneficial results and can be a useful approach in the medical management of urinary stones. A variety of compounds have been investigated to curtain endogenous oxalate synthesis which is a crucial factor, most of these compounds have not proved to be effective in the in vivo situation and some of them are not free from the toxic effect. The non-operative management of stone disease has been practiced in ancient India in the three famous indigenous systems of medicine, Ayurveda, Unani and Siddha, and proved to be effective.However the efficiency of most of these substances is still questionable and demands further study. Man as well as other mammals cannot metabolize oxalic acid. Excessive ingestion of oxalic acid can arise from oxalate rich food and from its major metabolic precursors, glycollate, glyoxylate and ascorbic acid can lead to an acute oxalate toxicity. Increasedlevels of circulating oxalate, which can result in a variety of diseases including renal failure and oxalate lithiasis. The ability to enzymatically degrade oxalate to less noxious Isubstances, formate and CO2, could benefit a great number of individuals including those afflicted with hyperoxaluria and calcium oxalate stone disease.

Two novel bis-azomethines derived from quinoxaline-2-carbaldehyde

The Schiff base compounds N,N0-bis[(E)-quinoxalin-2-ylmethylidene] propane-1,3-diamine, C21H18N6, (I), and N,N0-bis[(E)- quinoxalin-2-ylmethylidene]butane-1,4-diamine, C22H20N6, (II), crystallize in the monoclinic crystal system. These molecules have crystallographically imposed symmetry. Compound (I) is located on a crystallographic twofold axis and (II) is located on an inversion centre. The molecular conformations of these crystal structures are stabilized by aromatic pye stacking interactions.