The characteristics of seventy-six calixarene crystal structures derived from the Cambridge Crystallographic Database are presented. This survey is a discussion of the inter and intramolecular effects on the solid state cavity shape and molecular recognition ability of the compounds. In addition to this survey, four new calixarene crystal structures are presented. The conformational characteristics of these four calixarenes are determined by a complicated array of inter and intramolecular interactions in the crystal packing.
The focus of this research is to explore the molecular-level interactions between reactive metal surfaces and aqueous environments by combined ultra-high vacuum/electrochemistry (UHV-EC) methodology. The objectives of this work are to understand (1) the effects of sulfate ions on the passivity of metal oxide/hydroxide surface layer, (2) the effects of sulfur-modification on the evolution of metal oxide/hydroxide surface layer, and (3) the effects of sulfur adsorbate on cation adsorption at metal surfaces.
Dissertation research involves development of Mobile Order Theory thermodynamic models to mathematically describe and predict the solubility, spectral properties, protonation equilibrium constants and two-phase partitioning behavior of solutes dissolved in binary solvent mixtures of analytical importance. Information gained provide a better understanding of solute-solvent and solvent-solvent interactions at the molecular level, which will facilitate the development of better chemical separation methods based upon both gas-liquid and high-performance liquid chromatography, and better analysis methods based upon complexiometric and spectroscopic methods. Dissertation research emphasizes chemical equilibria in systems containing alcohol cosolvents with the understanding that knowledge gained will be transferable to more environmentally friendly aqueous-organic solvent mixtures.
Experimental mole fraction solubilities of benzil, thianthrene, trans-stilbene, thioxanthen-9-one, diphenyl sulfone and dibenzothiophene sulfone are determined in pure noncomplexing and complexing solvents. Predicted solubility values are calculated for benzil, thianthrene, trans-stilbene and thioxanthen-9-one using expressions derived from Mobile Order theory. Large deviations between experimental and predicted solubilities in alcohol solvents exist, therefore optimized solute - solvent association constants are determined. Previously measured thianthrene solubilities in five binary alkane + cyclohexane solvent mixtures are compared with values predicted from Mobile Order theory using the measured solubility in each of the pure solvents as input parameters. The experimental mole fraction solubility of benzil in eight binary alcohol + 1-octanol solvent mixtures are also measured and compared with predicted values.
The purpose of this investigation is to make more detailed studies of transformations. Fourteen compounds have been examined by high temperature X-ray diffraction for this purpose. The investigations have been carried out in such a way as to reveal: 1. the existence of transformations, 2. the influence of polarizability on thermal expansion, 3. the anisotropy of expansion, and 4. the discontinuity of thermal expansion.
The focus of the following research was to (1) understand the chemistry involved in nitriding an organosilicate glass substrate prior to tantalum deposition, as well as the effect nitrogen incorporation plays on subsequent tantalum deposition and (2) the reduction of a native oxide, the removal of surface contaminants, and the etching of a HgCdTe surface utilizing atomic hydrogen. These studies were investigated utilizing XPS, TEM and AFM. XPS data show that bombardment of an OSG substrate with NH3 and Ar ions results in the removal of carbon species and the incorporation of nitrogen into the surface. Tantalum deposition onto a nitrided OSG surface results in the initial formation of tantalum nitride with continued deposition resulting in the formation of tantalum. This process is a direct method for forming a thin TaN/Ta bilayer for use in micro- and nanoelectronic devices. Exposure to atomic hydrogen is shown to increase the surface roughness of both air exposed and etched samples. XPS results indicate that atomic hydrogen reduces tellurium oxide observed on air exposed samples via first-order kinetics. The removal of surface contaminants is an important step prior to continued device fabrication for optimum device performance. It is shown here that atomic hydrogen effectively removes adsorbed chlorine from the HgCdTe surface.
NiSi and Ni(Pt)Si, and of the effects of dissociated ammonia on oxide reduction was carried out under controlled ultrahigh vacuum (UHV) conditions. X-ray photoelectron spectroscopy (XPS) has been used to characterize the evolution of surface composition. Vicinal surfaces on NiSi and Ni(Pt)Si were formed in UHV by a combination of Ar+ sputtering and thermal annealing. Oxidation of these surfaces in the presence of either O+O2 or pure O2 at room temperature results in the initial formation of a SiO2 layer ~ 7 Å thick. Subsequent exposure to O2 yields no further oxidation. Continued exposure to O+O2, however, results in rapid silicon consumption and, at higher exposures, the kinetically-driven oxidation of the transition metal(s), with oxides >35Ǻ thick formed on all samples, without passivation. The addition of Pt retards but does not eliminate oxide growth or Ni oxidation. At higher exposures, in Ni(Pt)Si surface the kinetically-limited oxidation of Pt results in Pt silicate formation. Substrate dopant type has almost no effect on oxidation rate. Reduction of the silicon oxide/metal silicate is carried out by reacting with dissociated NH3 at room temperature. The reduction from dissociated ammonia (NHx+H) on silicon oxide/ metal silicate layer shows selective reduction of the metal oxide/silicate layer, but does not react with SiO2 at ambient temperature.
The theoretical model of Beratan and Onuchic predicts a large attenuation of ET rates through hydrogen bonds; however, the effect of individual hydrogen bond on electron transfer reaction has not been systematically studied. The organic complexes in this study are a series of crown ether/ammonium salt, which incorporate a redox partner on each component of the complex. The dimethoxynaphthalene redox donor was attached to the crown ether and a series of ammonium salts was synthesized which bear substituted quinone and naphthoquinone acceptor. The complexes characterization and preliminary electron transfer rate measurement were completed with UV/Vis and steady-state emission spectroscopy.
Electrodeposition of diamond-like carbon (DLC) films was studied on different substrates using two different electrochemical methods. The first electrochemical method using a three-electrode system was studied to successfully deposit hydrogenated DLC films on Nickel, Copper and Brass substrates. The as-deposited films were characterized by scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), fourier transform infrared spectroscopy (FTIR) and cyclic voltammetry (CV). A variety of experimental parameters were shown to affect the deposition process. The second electrochemical method was developed for the first time to deposit hydrogen free DLC films on Ni substrates through a two-electrode system. The as-deposited films were characterized by Raman spectroscopy and FTIR. According to Raman spectra, a high fraction of diamond nanocrystals were found to form in the films. Several possible mechanisms were discussed for each deposition method. An electrochemical method was proposed to deposit boron-doped diamond films for future work.
A Series of fluorophores of the general formular P(CF2)nP and P(CF2)n-1CF3 has been synthesized. Copper catalyzed coupling of 1-bromopyrene and the corresponding mono and di-iodoperfluoroalkanes were used in most cases. For the n=3 dimer, a novel 1,w-perfluoroalkylation of pyrene via bis-decarboxylation of hexafluorogultaric acid was utilized. These compounds, along with suitable hydrocarbon analogs, are being used to study the flexibility of fluorocarbon chains using emission. We have found that the excimer formation for the fluorinated pyrene monomers is highly dependent on concentration and is less efficient than for pyene. Excimer formation for the fluorinated pyrene dimers is much more efficient than for the fluorocarbon monomers and is only slightly concentraion dependent. Steady-state emission spectra indicate hydrocarbon dimers-models form excimers more efficiently than the fluorinated dimers suggesting the fluorinated chains are stiffer than the hydrocarbons. We conducted the temperature-dependent studies and quantified the conformational difference.
The initial purpose of this study was to determine if steric problems would account for the difference in the products obtained in the reaction of the N-(substituted)phthalimide with low and high molecular weight amines.
The purpose of the investigation described herein was to investigate the degree of delocalization of the unpaired electron in ion radicals formed in the oxidation process of compounds with aromatic rings connected by means of various groups and atoms not entering the ring; then, to establish the relationship of coupling constants in radical cations with substituent σ values. The parent cation radical, in which the co-planar ion was derived from N,N-dimethylaniline, was selected in order to maximize the substituent effects on coupling constants and to obtain couplings at several positions (specifically, CH3, N, and ring protons).
In an effort to study the spectral, magnetic, and stereochemical properties of vanadyl complexes, both a new series of vanadyl complexes derived from type (VII) ligands with subnormal magnetic moment and from type (VIII) ligands with normal magnetic moment are synthesized and characterized.
In many series of compounds, intensity of biological activity and chemical reactivity are proportional. Generally whenever a alkyl group replaces a reactive hydrogen atom, as would be the case for an N-substituted hydroxylamine as compared to hydroxylamine, the over-all biological activity of the resulting compound is lower than that of its nonalkylated analogue. Since toxicity and physiological activity are not proportional, this comparison can only suggest possible types of derivatives to prepare and test.
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.
The oxidative elimination reactions of (5-X-phen)Mo(C0)₄ (X = H, CH₃, Cl, NO₂; phen = o-phenanthroline) and (3,4,7,8-(CH₃)₄-phen)Mo(CO)₄ with mercuric chloride in acetone have been investigated. In these reactions, a carbon monoxide group is replaced by two univalent ligands, accompanied by the corresponding increase in coordination number and formal oxidation state of the central metal atom, to give products of the type, (X-phen)Mo(CO)₃(Cl)HgCl. With the exception of (3,4,7,8-(CH₃)₄-phen), the substituted o-phenanthrolines were selected so as to minimize steric differences from one substrate to another while obtaining the widest range of pKₐ of the ligand.
The recombination rate coefficient for molecular helium ions has been measured in a pulsed afterglow at 1.86 Torr as a function of electron temperature and electron density without making a priori assumptions about the functional dependence. The concentrations of the molecular ions and electrons were measured and the source terms for the molecular ions were included in the rate equation.
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.
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 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.
At the time this work was begun, there was some confusion about the technique necessary for the successful synthesis of organomagnesium compounds in hydrocarbon solvents and without solvents. It was decided to repeat the work of Bryce-Smith and Zakharkin. Thus began the study of the synthesis of organomagnesium compounds without solvents; the study of the reaction products of these organomagnesium compounds in hydrocarbons plus 2-butanone compared to the reaction products of the corresponding etheral Grignard reagent plus 2-butanone; and a preliminary study of the nature of these organomagnesium compounds in hydrocarbon solvents.
Detection, identification and separation of polycyclic aromatic compounds in environmental samples are of extreme importance since many of these compounds are well known for their potential carcinogenic and/or mutagenic activities. Selective quenching of molecular fluorescence can be utilized effectively to analyze mixtures containing different polycyclic aromatic hydrocarbons. Molecularly organized assemblies are used widely in detection and separation of these compounds mainly because of less toxicity and enhanced solubilization capabilities associated with these media. Feasibility of using nitromethane and the alkylpyridinium cation as selective fluorescence quenching agents for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons (PAHs) is critically examined in several molecularly organized micellar solvent media. Fluorescence quenching is used to probe the structural features in mixed micelles containing the various combinations of anionic, cationic, nonionic and zwitterionic surfactants. Experimental results provide valuable information regarding molecular interactions between the dissimilar surfactants.
Pulsed laser flash photolysis with both visible and infrared detection has been applied to the study of the displacement of weakly coordinating ligands (Lw) by strongly "trapping" nucleophiles (Ls) containing either an olefinic functionality (Ls = 1-hexene, 1-decene, 1-tetradecene) or nitrogen (Ls = acetonitrile, hydrocinnamonitrile) from the photogenerated 16 electron pentacarbonylchromium (0) intermediate. 5-Chloropent-l-ene (Cl-ol), a potentially bidentate ligand, has been shown to form (ol-Cl) pentacarbonylchromium (0), in which Cl-ol is bonded to Cr via a lone pair on the chlorine, and isomerize to (Cl-ol) pentacarbonylchromium (0), in which Cl-ol is bonded to the olefinic functionality on the submillisecond time scale. This process has been studied in both the infrared and visible region employing both fluorobenzene or n-heptane as the "inert" diluent. Parallel studies employing 1-chlorobutane and 1-hexene were also evaluated and showed great similiarity with the Cl-ol system. The data supported a largely dissociative process with a possibility of a small interchange process involving the H's on the alkyl chain. Studies were also carried out for various Cr(CO)6/arene/Ls systems (arene = various alkyl or halogenated substituted benzenes). The data indicated that for both C6H5R (R=various alkyl chains) or multi-alkyl substituted arenes (i.e. o-xylene, 1,2,3-trimethylbenzene) containing an "unhindered" ring-edge, bonding to the the Cr(CO)5 moiety occurs "edge on" via a partially delocalized center of unsaturation on the ring. The data indicated that both electronic and steric properties of the arenes influence the kinetics, and that an interchange pathway takes place at least, in part, through the alkyl chains on both the arenes and "trapping" nucleophiles. Moreover, halogenated arenes bond through the lone pair on the halogen for both CI- and Br- derivatives but "edge-on" for the fluorinated arenes. Finally, in the case of arene complexes without and "unhindered" ring-edge (i.e., 1,2,3,4,5-pentamethylbenzene) bonding can occur either "edge-on" or through the ring ...
The purpose of this piece of research is to determine the chemical composition of soft winter wheat, and to make a comparative study of it. A study is also made concerning its possibilities as a balanced food.
A study was conducted to investigate the relationships between cybergaming treatment groups and the control group (N = 99: ncontrol = 8; nlogic = 29; nspatial = 30; ncombination = 32) with success in the organic chemistry I course as measured by achievement over a 10-week period. The treatment groups included logic training, spatial training, and combination logic-spatial training. Students' ability was measured by pre/post exams using the Group Assessment of Logical Thinking (GALT) to measure logic ability, Purdue Visualizations of Rotations (ROT) test to measure spatial skills, and the General-Organic-Biochemistry (GOB) Exam to measure content attainment. Finally, students' responses about participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. A second study was conducted to evaluate the relationship between the cybergaming treatment and control groups (N = 88: nexperimental = 27; ncontrol = 61) with success in the general chemistry I course as measured by achievement and final course averages and grades. The cybergaming treatment group underwent intensive combination logic-spatial training for 10 weeks. Students' progress was measured using three pre/post instruments: Group Assessment of Logical Thinking (GALT) measured logic ability, Purdue Visualizations of Rotations (ROT) Test measured spatial skills, and the California Chemistry Diagnostic Exam measured content attainment. Finally, students' responses about their participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. Analyses of the data were performed to determine the relationships between cybergaming treatments and control groups in organic chemistry I and general chemistry I courses. In organic chemistry I results showed no statistical or practical significance as to students' success. In general chemistry I results indicated statistical significance and medium practicality for students with an average grade of C and for females over males as to improvement of spatial skills.
The purpose of this work is to make a fairly complete chemical analysis of the Mebane 804-50 cottonseed kernel. A brief history of cotton plant and the economic value of its products are also presented.
The purpose of this research problem is to determine the chemical composition of the blackeyed pea and to make a comparative study of the results. The value of the blackeyed pea as food, its chemical nature, and possible industrial uses are studied and recorded.
The acid which is analogous to the next member of the diphenylpolyenes, 1,4-diphenylbutadiene, is muconic acid. This acid has been chosen to be investigated in an effort to isolate all the stereoisomers of a set containing more than two isomers.
Aluminum was deposited onto both Teflon AF and Parylene AF surfaces by chemical vapor deposition of trimethylaluminum. This work shows that similar thin film (100 Angstroms) aluminum oxide adlayers form on both polymers at the low temperature dosing conditions used in the studies. Upon anneal to room temperature and above, defluorination of the polymer surfaces increased and resulted in fluorinated aluminum oxide adlayers; the adlayers were thermally stable to the highest temperatures tested (600 K). Angle-resolved spectra showed higher levels of fluorination toward the polymer/adlayer interface region. Copper films were also deposited at low temperature onto Teflon AF using a copper hexafluoroacetylacetonate-cyclooctadiene precursor. Annealing up to 600 K resulted in the loss of precursor ligands and a shift to metallic copper. As with aluminum adlayers, some polymer defluorination and resulting metal (copper) fluoride was detected. Parylene AF and polystyrene films surfaces were modified by directly dosing with water vapor passed across a hot tungsten filament. Oxygen incorporation into polystyrene occurred exclusively at aromatic carbon sites, whereas oxygen incorporation into parylene occurred in both aromatic and aliphatic sites. Oxygen x-ray photoelectron spectra of the modified polymers were comparable, indicating that similar reactions occurred. The surface oxygenation of parylene allowed enhanced reactivity toward aluminum chemical vapor deposition. Silicon-carbon (Si-Cx) films were formed by electron beam bombardment of trimethylvinylsilane films which were adsorbed onto metal substrates at low temperatures in ultra-high vacuum. Oxygen was also added to the films by coadsorbing water before electron beam bombardment; the films were stable to more than 700 K, with increasing silicon-oxygen bond formation at elevated temperatures. Copper metal was sputter deposited in small increments onto non-oxygenated films. X-ray photoelectric spectra show three-dimensional copper growth (rather than layer-by-layer growth), indicating only weak interaction between the copper and underlying films. Annealing at elevated temperatures caused coalescence or growth ...
A combined experimental and computational study on the reversible ortho-metalation exhibited by the triosmium cluster Os3(CO)10(dppm) (dppm = 1,1-bis(diphenylphosphino)methane is reported. The conversion of nonacarbonyl cluster HOs3(CO)9[-PhP(C6H4)CH2PPh2] to Os3(CO)10(dppm) is independent of added CO and exhibits a significant inverse equilibrium isotope effect (EIE). Reductive coupling of the C-H bond in HOs3(CO)9[-PhP(C6H4)CH2PPh2] leads to the formation of agostic C-H and two distinct aryl-π species prior to the rate-limiting formation of the unsaturated cluster Os3(CO)9(dppm). Heating the unsaturated dimer H2Re2(CO)8 with Cp*Rh(CO)2 (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene) at elevated temperature affords the new trimetallic clusters H2RhRe2Cp*(CO)9 and HRh2ReCp*2(CO)6, and the spiked-triangular cluster HRhRe3Cp*(CO)14. H2Re2(CO)8 reacts with Cp*2Rh2(CO)2 under identical conditions to furnish H2RhRe2Cp*(CO)9 and HRh2ReCp*2(CO)6 as the principal products, in addition to the tetrahedral cluster H2Rh2Re2Cp*2(CO)8. H2RhRe2Cp*(CO)9 undergoes facile fragmentation in the presence of halogenated solvents and the thiols RSH (where R = H, C6H4Me-p) to afford the structurally characterized products Cp*Rh(-Cl)3Re(CO)3, S2Rh3Cp*(CO)4, Cp*Rh(-Cl)(-SC6H4Me-p)2Re(CO)3, and Cp*Rh(-SC6H4Me-p)3Re(CO)3. The new hydrazido-substituted compounds TaCl(NMe2)3[N(TMS)NMe2] (TMS = tetramethylsilyl) and Ta(NMe2)4[N(TMS)NMe2] have been synthesized and their structures established by X-ray crystallography. The latter product represents the first structurally characterized octahedral tantalum(V) complex containing a single hydrazido(I) ligand in an all-nitrogen coordinated environment about the metal center. The fluxional properties of the amido and hydrazido ligands in these new compounds have been established by VT 1H NMR spectroscopy (VT = variable temperature). Preliminary data using Ta(NMe2)4[N(TMS)NMe2] as an ALD (ALD = atomic layer deposition) precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.
Preparative mass spectrometry is an important method for the synthesis of new materials. Recently, soft landing mass spectrometry has been used to land ions on surfaces to coat or otherwise alter them. Commercial soft landing instruments do not yet exist, and the physical phenomenon of soft landing has not yet been fully described. For future ion mobility soft landing research, the theory of ion mobility, ion optics and soft landing is discussed, and 2 soft landing instruments have been built and described, along with proof of concept experiments for both instruments. Simulations of the process of ion mobility and ion optics for use in these instruments, as well as some preliminary results for the optics are included. Surfaces described include copper on mica and iron on silicon. Self assembly of soft landed ions is observed on the surfaces. The instruments constructed will be useful for future soft landing research, and soft landing can be used for future materials research with special attention focused on the self-assembly of the landed ions.
In recent years, advances in computer technology combined with new ab initio computational methods have allowed for dramatic improvement in the prediction of energetic properties. Unfortunately, even with these advances, the extensive computational cost, in terms of computer time, memory, and disk space of the sophisticated methods required to achieve chemical accuracy - defined as 1 kcal/mol from reliable experimental data effectively - limits the size of molecules [i.e. less than 10-15 non-hydrogen atoms] that can be studied. Several schemes were explored to help reduce the computational cost while still maintaining chemical accuracy. Specifically, a study was performed to assess the accuracy of ccCA to compute atomization energies, ionization potentials, electron affinities, proton affinities, and enthalpies of formation for third-row (Ga-Kr) containing molecules. Next, truncation of the correlation consistent basis sets for the hydrogen atom was examined as a possible means to reduce the computational cost of ab initio methods. It was determined that energetic properties could be extrapolated to the complete basis set (CBS) limit utilizing a series of truncated hydrogen basis sets that was within 1 kcal/mol of the extrapolation of the full correlation consistent basis sets. Basis set truncation for the hydrogen atom was then applied to ccCA in the development of two reduced basis set composite methods, ccCA(aug) and ccCA(TB). The effects that the ccCA(aug) and ccCA(TB) methods had upon enthalpies of formation and the overall percent disk space saved as compared to ccCA was examined for the hydrogen containing molecules of the G2/97 test suite. Additionally, the Weizmann-n (Wn) methods were utilized to compute the several properties for the alkali metal hydroxides as well as the ground and excited states of the alkali monoxides anion and radicals. Finally, a multi-reference variation to the correlation consistent Composite Approach [MR-ccCA] was presented and utilized in the computation ...
A series of new planar complexes with the dianion of 2,3-quinoxalinedithiol ligand has been prepared. The complexes have been characterized from the study of their analyses, magnetic moment, conductance, polarograms, electron spin resonance spectra, and electronic spectra, and compared with the available data on the corresponding maleonitriledithiolene and toluene-3,4-dithiolene complexes.
Because of the need for data on the geometry of nitrogen in arylamines, the determination of the crystal and molecular structures of tri-(p-fluorophenyl)-amine (TFPA) and tri-(p-iodophenyl)-amine (TIPA) was undertaken as the subject of this dissertation.
That Lactobacillus arabinosus 17-5, ATCC 8014, can supply its own requirement for the amino acid, lysine, is demonstrated by the fact that the organism is capable of growth in media devoid of lysine. Since the final biosynthetic step in lysine formation in all bacteria studied to date involves the decarboxylation of meso-dlaminopimelic acid (DAP) to produce lysine, it was of interest to determine whether an enzyme catalyzing such a reaction (DAP decarboxylase) is present in L. arabinosus.
The pyrolysis of sec-butyllithium in solution was studied in an attempt to understand the loss of stereo-specificity and the atypical kinetics that have been reported. Additionally, the effect of added lithium alkoxides was studied to determine their effects on the highly reactive sec-butyllithium substrate.
Since Djerassi and Scholz found that 2-(aryloxy-methyl)imidazolines and their hydrochloride salts exhibit vasoconstrictive properties, the 1,2-(I) 1,3-(II) and 1,4-bis-(2-imidazolinylmethoxy) benzene (III) analogs (Fig. 1, p.2) were chosen for synthesis in order to test them for their effective vasoconstrictive characteristics and for whatever other physiological properties they might exhibit.
It was proposed to study the cycloaddition of ketenes and carbodiimides in some detail. The first objective was to investigate the general applicability of the reaction as a tool for the synthetic organic chemist in the preparation of a new class of substituted β-lactams; i.e., imino-β-lactams. It was proposed for this part of the research problem to look for the intermediate, either directly or indirectly, by trapping experiments. It was further proposed to study substituent effects in the ketene and carbodiimide and also Investigate the effect of solvent polarity on the reaction rate. From these data, it was hoped that the mechanism of the cycloaddition reaction could be elucidated.
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.
With three different proposals for the bonding in metal carbonyls, it was decided to look into the situation more thoroughly in order to see what other evidence was available to support or refute any of these ideas. It became obvious that a definite contradiction existed between the kinetic evidence of various metal carbonyls, and the concept of MC bond strengths as predicted by Cotton's theory.
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