Physical Sciences and Mathematics Commons^™

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclobutyl Derivatives, Hao Ku

Masters Theses

A study was initiated on the hypothesis, by Ugi and co-workers, that cyclopropyl, cyclobutyl, and cyclopentyl electrophiles might under go nucleophilic substitution reactions with retention of configuration.

The synthesis of benzocyclobutenol and 2-phenylcyclobutyl tosylate is described. The reactions of these tosylates with cobalt(I) "supernucleophiles" gave low yields of products which have not been purified sufficiently for assignment of stereochemistry.

Reaction of cyclopentyl tosylate and phenylethyl tosylate with the "supernucleophiles" cobaloxime(I) and cobalt(salen)(I) is discussed for the advance of future work.

Reactions Of Tungsten Carbonyl Complexes Containing Diphenylvinylphosphine, George S. Leotsakos

Masters Theses

A new synthetic route for the production of the tungsten carbonyl complex (OC)₅WPPh₂CH₂CH₂PPh₂ has been discovered. It has been found that lithiumdiphenylphosphide reacts with diphenylvinylphosphinepentacarbonyltungsten(0) in tetrahydrofuran to produce upon hydrolysis a good yield of the pentacarbonyl product […]. No evidence for the formation of secondary products was noted nor was there evidence for preferential attack of the carbonyl group by LiPPh₂ to form a carbene complex.

Diphenylvinylphosphinepentacarbonyltungsten(0) (mp 62-64°C), was prepared for the first time by two different methods.

I. Displacement of aniline from anilinepentacarbonyltungsten(0) complex with diphenylvinylphosphine.

II. …

The Intramolecular Torsional Potential And Dielectric Properties Of 2,3-Butanedione, Gevert H. Meyer

Masters Theses

Dipole moment measurements have been carried out on 2,3-butanedione in solution, pure liquid, and the vapor phase. A dipole moment of 1.03 ± .01 Debye was observed for dilute solutions of 2,3-butanedione in carbon tetrachloride. Pure liquid samples exhibit an anomalous dipole of 1.56 ± .01 Debye. The following results were obtained for vapor phase measurements: 1.04, 1.07, 1.08, 1.11, and 1.17 ± .01 Debye at 310.15, 350.15, 370.15, 431.70 and 472.10 ± .02°K respectively.

The acetyl torsional potential was characterized from the observed temperature dependence of dipole moment. This torsional mode was described by a two-parameter potential function: V(Ø) …

Studies Of Acetylcholinesterase In Synaptosomes, Syed Abbas Rizvi

Masters Theses

Acetylcholinesterase from rat brain was studied in crude homogenates, partially purified enzyme fractions, and in synaptosomes, to observe modification of the enzyme as a consequence of the modification of the membrane containing it.

Sodium dodecyl sulfate decreases the absorbance due to particles in the homogenate. This change in absorbance was proportional to both the concentration of sodium dodecyl sulfate and the concentration of the particles. Further, sodium dodecyl sulfate caused sulfhydryl groups to appear in the crude homogenate and in partially purified enzyme fractions. Synaptosomal preparations did not give such results. At concentrations of sodium dodecyl sulfate sufficient to cause …

Mechanistic Studies Of Alkylation Of Cobalt(I) By Cyclopropyl Derivatives, Lailing Magdalene Soong

Masters Theses

A second order nucleophilic substitution reaction with retention of configuration is predicted by Ugi and co-workers if electrophiles such as cyclopropyl, cyclobutyl, or cyclopentyl derivatives undergo substitution under conditions where the S_N2 process is faster than the competing S_N1 process.

A synthesis of both cis and trans-7-chlorobicyclo [4.1.0] heptane from olefin and dichlorocarbene is described. The compound, bicyclo [4.1.0] heptylpyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(III), which contains an alkylcobalt σ-bond, is obtained from the reaction of pyridine [bis(salicylaldehyde)ethylenediiminato] cobalt(I) and 7-chlorobicyclo [4.1.0] heptane. The great light sensitivity of this compound has prevented its isolation in purity sufficient for nmr …

Zwitterionic Carbonyl Halide Complexes Of Tungsten, Dragoslav Marcovich

Masters Theses

The first carbonyl halide zwitterionic complexes have been synthesized and are of the type cis- (OC)₄XWPPh₂(CH₂)nPPh₂R in which X is Cl, Br, or I, n is 1 or 2, and R is an alkyl group. The complexes were prepared by the reaction […]. The temperature of the reaction must be carefully controlled since the decomposition point of the product is only 10°C higher than that of the reactant.

The zwitterionic complexes are sensitive to light in solution but are insensitive to light in the solid state. Unlike carbonyl halide complexes of the …