The site of initial metal-carbonyl bond-breaking during ligand-exchange reactions in a series of octahedral metal carbonyls of the type (L2)M(CO)4 (M = Cr, Mo, W; L2 = diphos, phen, dipy) has been determined employing infrared spectroscopy and Fourier transform nuclear magnetic resonance spectroscopy. The results of this study reveal, for all metal carbonyl complexes of the type mentioned above, that loss of CO occurs exclusively at an axial position (cis to the bidentate ligand, I^)• The dynamic nature of the five-coordinate intermediates, such as (diphos)Mo(CO)3, (phen)M(CO)3 (M = Cr, Mo, W), and (dipy)Cr(CO)3, which are generated in solution upon CO dissociation, is reported and discussed. The results of this investigation confirm that these intermediates are fluxional on the time scale of CO-exchange process. A mechanism which describes the site of initial metal-carbonyl bond-breaking and the fluxionality of the five-coordinate intermediate during ligand-exchange reactions in the complexes (L2)M(CO)4 is proposed. A kinetic study of reactions of W(CO)6 with pseudo-halide anions (NCS-, NCO-, CN-) has been initiated. The results indicate that these reactions proceed via a bimolecular path, which involves initial attack of the pseudo-halide anion at a carbonyl carbon of W(CO)6,

Many of the bands in the vapor-phase far-ultraviolet absorption spectra of simple molecules can often be fit to mathematical progressions referred to as molecular Rydberg series. The name Rydberg arises from the similarity between the Rydberg formula for the atomic hydrogen spectrum and the formulae for the progressions found in molecular spectra. The theories of molecular Rydberg transitions and states are discussed in terms of the inferences that have been made in the past from the available spectral data. The dipole moment changes (ca. 0.4 Debye units) from the ground state to all of the Rydberg states studied were found to be smaller than changes typically found in transitions of charge-transfer nature (ca. 1 Debye unit). The implication is that the Rydberg transitions are fairly localized. The changes in polarizability are on the order of 6 x 10⁻²⁴ cm³ and are assumed to be increases over those of the ground state.

This investigation involved the synthesis of 1-amino-2-hydroxycyclopentanecarboxylic acid, a potential structural analog of the natural amino acids, serine and threonine. The title compound also includes the structural features present in an established antitumor agent, cycloleucine.

Four isosteric series of plant growth-regulating compounds were prepared. Using an Avena sativa coleptile assay system, derivatives in series I and IV inhibited segment elongation to a greater degree than did comparable derivatives in series II and III.

Part I describes the addition of several acid chlorides to dimethylketene. The resulting 3-ketoacid chlorides were isolated and characterized. Part II describes the cycloaddition of several aldoketenes to chloral. The ketenes were generated in situ by dehydrohalogenation and dehalogenation of appropriately substituted acyl halides.

Pyridine ring analogs of the aromatic amino acids phenylalanine and tyrosine were synthesized and studied in microbiological and mammalian systems.

The purpose of the present work is to study the effects of the trimethylsilyl and trimethylgermyl substituents on the N,N-dimethylamino ring system. Both ground and excited state interactions were studied and their magnitudes determined. The experimental data were then used in conjunction with molecular orbital calculations to differentiate among, and determine the importance of, d-p bonding, hyperconjugation or polarization of the trimethylsilyl group on the ground and excited state bonding.

This thesis reports the synthesis and characterization of two new copper(II) halide complexes with deprotonated N-(2-hydroxyethyl)ethylenediamine behaving as a bidentate. The magnetic properties of the new copper(II) complexes were studied from room temperature to liquid nitrogen temperatures. The magnetic data show that both complexes exhibit antiferromagnetic interactions with a singlet ground state and a thermally accessible triplet excited state. Magnetic data and infrared spectra indicate the complexes are halogenbridged. Deprotonation at an amine nitrogen is based on the presence of a hydroxyl stretching band in the infrared spectra. Electronic spectra and infrared spectra indicate the complexes are square planar. Elemental analyses, infrared spectra, electronic spectra, electron spin resonance spectra, and magnetic data are reported and discussed.

In this work magnetic properties of copper(II) complexes on N-(hydroxyalkyl) pyrrole-2-aldimines were investigated by various techniques, one of which was magnetic susceptibility. Magnetic moments are not directly determined experimentally, but magnetic susceptibilities are.

A paucity of literature exists on the Independent System analysis of adjacent, parallel transition dipoles. Applying this theory and certain spectral information semiemperical calculations were made to predict absorption profiles and band intensities. To aid in the assignment of the 7*+7 absorption bands it was necessary to obtain the vacuum ultraviolet spectra of cyclohexane and cyclohexene. Because the spectra of these molecules contained sharp, atomic-like absorption bands a Rydberg series could be fitted to certain absorptions, thus the determination of their ionization potentials. Using Independent System analysis profiles and intensities of 7*+q-- absorption bands ins 'several methyl substituted 1,4- cyclohexadienes and isotetralin were predicted where general agreement was found with observed experimental spectra.

The present study has resulted in the development of a procedure for the specific chemical fragmentation of human phosphoglucose isomerase into a minimal number of peptides. A two-cycle procedure for cleaving the protein with 2-nitro-5- thiocyanobenzoic acid results in four primary peptides and three overlap peptides. The peptides can be readily separated on the basis of their size by using sodium dodecyl sulfate polyacrylamide gel electrophoresis. Preliminary peptide alignments have been considered, and amino acid analyses have been performed. End-terminal analyses of the enzyme revealed a carboxyl terminal sequence of Asp-Val-Gln and a blocked amino terminus. The cysteine cleavage procedure provides an excellent method for the identification and location of specific genetic mutations of human phosphoglucose isomerase.

The biological activities of some homeosterically related analogs of dihydrofolic acid have been examined involving pyrimido[4,5-b][l,4]oxazine (8-oxapteridine) derivatives. It is anticipated that these compounds might interfere with the essential intermediary metabolic functions of the vitamin and thus serve as potential chemotherapeutic agents. Preliminary toxicity studies in microbial assay systems were disappointing; however, inhibitory effects were demonstrated in cell free enzyme systems. A comparison of the structure/activity relationships was determined using two folic acid coenzyme systems, dihydrofolate reductase and thymidylate synthetase. The 2-amino-4-hydroxy-6-(substituted)-8-oxapteridines were generally more effective inhibitors than the corresponding 2,4-diamino analogs. The relative biological activity of a series of 2-amino-4-hydroxy-6-ω-phenylalkyl derivatives were examined, and the most active derivative was the 6-phenylethyl analog which appears to function as a mixed-type inhibitor involving partially competitive and partially non-competitive inhibition.

The correlation between the carbon-proton and proton-proton coupling constants have been studied in various 13 systems. Isocrotonic acid-carboxyl-3C, crotonic acid- 13 13 carboxyl-3C, and 5-norbornene-2-carboxylic acid-carboxyl-3C- 1,5,6,7,7-hexachloro were synthesized and their carbonproton coupling constants were analyzed. Nmr studies showed the magnitudes of the carbon-proton coupling constants to correlate well with analogous protonproton coupling constants, although the values of the couplings were larger than expected. The geminal olefinic couplings were considerably larger than all other couplings, but they were self-consistent. The signs of the carbon-proton coupling constants also were in agreement without exception with the signs of analogous proton-proton coupling constants.

Structural properties of phosphoglucose isomerases isolated from a variety of species have been compared by peptide fingerprinting, predicted amino acid sequence homologies and by denaturation and renaturation studies. The enzymes are more readily denatured in guanidinium chloride than in urea, and the isomerase isolated from yeast is more stable toward acid pH than the rabbit muscle enzyme. The rates of guanidinium chloride-induced denaturation are markedly increased by ionic strength and decreased by substrates, competitive inhibitors or glycerol. The enzyme can be renatured, but only in the presence of glycerol. The renaturation process is dependent on protein concentration and temperature and provides a method for the formation of mixed species heterodimers.

The study consists of three major areas of research. First, the dihedral angle dependence of vicinal carbon-carbon coupling constants is determined for aliphatic and alicyclic carboxylic acids wherein the formal hybridization and substituents are held constant. Second, the magnitudes and relative signs of long-range carbon-carbon coupling constants in a. triple- 13 C-labeled system are determined and compared with carbon-proton and/or proton-proton coupling constants in geometrically similar compounds. Third, the effect of changes in hybridization on long-range carbon-carbon coupling constants is determined for the following three groups of molecules: olefins and saturated hydrocarbons, aliphatic carboxylic acids, and aromatic compounds. In all cases only closely related systems are compared in order to identify the effect of individual molecular parameters. Most importantly, the results indicate that carbon-carbon couplings do correlate in magnitude and sign with carbon-proton and proton-proton couplings in analogous molecular. frameworks. Thus, the coupling mechanisms are similar in all three types of coupling. In addition, the observed trends in long-range carbon-carbon couplings provide an unambiguous method for assigning carbon chemical shifts.

This research is concerned with determining whether the previously reported synthesis of tropolone by the solvolysis of the dichloroketene-cyclopentadiene adduct in sodium acetate and acetic acid could be used to prepare 2-alkyltropones from the adducts of alkylhaloketenes and cyclopentadiene. The information obtained from these rearrangements could be useful in determining the mechanism of the ring expansion of halogenated ketene-cyclopentadiene adducts to tropone derivatives.

The structures of the new pyrethroids were elucidated utilizing nuclear magnetic spectroscopy and elemental analysis. The biological activity of the pyrethroids has been evaluated for houseflies and yellow fever mosquitoes. A correlation of increase in rapid knockdown and toxicity with decrease in size of halogen has been made. The most effective compound, the difluorovinyl ester, has a toxicity of 123 times greater than pyrethrins. This degree of toxicity has not previously been reported for a 5-benzyl-3-furanmethyl ester. The relative lipophilicities of the dihalovinyl esters, Rm, have been determined by reverse phase partition chromatography. The R values for the dihalo esters correlate with their m effectiveness as rapid knockdown agents. The least lipophilic compound, the difluorovinyl ester, possessed the highest knockdown in this dihalovinyl ester series. The difluorovinyl ester has incorporated a high level of toxicity while maintaining excellent effectiveness as a knockdown agent against houseflies. This combination of high knockdown and high toxicity in a single compound has not been previously reported. Several other pyrethroids were synthesized and evaluated for knockdown and toxicity, in order to make specific comparisons with pyrethroids of known effectiveness. The replacement of the isobutenyl group of the chrysanthemates by the dihalovinyl group has been effective …