Three approaches to the study of hydration of polymeric ions in relation to that of analogous simple ions have been made as follows: In the first part of the thesis, information in sought regarding the hydration of polyions by evaluating the degree of dielectric saturation near the charged particles. Previously, this had been done only in the ease of isolated simple ions assumed to be point charges. Since the ionic atmosphere can never be removed from the polyions, even in very dilute solutions, the simple electrostatic field cannot be used in the evaluation of the extent of dielectric saturation. The dielectric constant has therefore been obtained directly as a function of the distance from the polyion from a solution of the Poisson-Boltzmann equation and previously published relations between dielectric constant and field intensity. The solutions have been obtained by numerical methods using a digital electronic computer. The Poisson-Boltzmann equation was solved by this method for the following models: simple ions, cylindrical polyions, spherical polyions and planar colloidal ions. The relative degrees of dielectric saturation were calculated and related to the relative extents of primary hydration for the different ionic models. The effect of dielectric saturation on the field and potential functions is also discussed for the various ion models. The second part of the thesis deals with solvent electrostriction and the determination of salting-out by polyelectrolytes. In order to interpret the experimental data obtained on the salting-out of non-electrolytes (argon, ethylene, d-1 leucine and benzamide) by polyelectrolytes (sodium polyphosphates, potassium polymethacrylate and poly-4-vinyl-N-n-butylpyridinium bromide), it was first found necessary to modify the existing salting-out theories for simple ions and a proposed theory for polymeric ions, by taking into account the effect of dielectric saturation of the solvent near the ions. Such effects are shown to be important in determining salting-out constants and, in fact, lead to the recognition of the necessity for taking into account the specific structure (e.g. effective radius) of the primary hydration shell. Other modifications to the theory are also suggested. In the modified salting-out theory referred to above, the radius of the primary hydration shell in required. The third part of the thesis therefore describes the evaluation of this parameter from experimentally measured apparent molar volumes for simple and polymeric ions. The significance of these apparent molar volumes in relation to the hydration of this polymeric and simple ions is also discussed.

The initial stages of electrochemical oxidation of nickel surfaces have been investigated with respect to (a) anodic formation and reduction characteristics of the thin oxide films; (b) chemical characterization of the films, e.g. determination of the active oxygen to nickel content and stoichiometry; (c) relation of the chemical and electrochemical properties of the oxide films to the kinetics of anodic oxygen evolution on the oxides; (d) investigation of the origin and significance of irreversibility in the processes of formation and reduction of the oxide films (hysteresis effects). Complementary comparative work has also been carried out on silver oxide electrodes where surface oxide films in at least two easily distinguishable valence states are involved, and at low temperatures the formation of a third oxide Ag 2O3 is indicated. Since electrochemical behaviour of an electrode depends significantly on the pre-history of the electrode and the nature of the surface oxide, much attention has been given to the preparation of electrodes in comparable states. This matter was found to be of particular importance in the studies on oxygen evolution kinetics at the oxidized nickel surfaces. The kinetic observations provided evidence in support of the ion-radical type of recombination step as rate-determining in oxygen evolution kinetics. This is in agreement with the conclusions derived from studies on the behaviour of bulk oxide material studied previously in this laboratory. The potentiostatic studies on the oxygen evolution reaction at nickel, oxidised nickel surfaces and at silver revealed inhibition effects (self-passivation) analogous to those found in anodic organic oxidations at the noble metals. Here, however, the inhibiting species, surface oxides, are directly involved in the overall reaction itself. A kinetic theory of the "self-passivation" effects is presented in general terms for various supposed oxidation states of the surface region of the electrode interphase. In order to relate the nature of the surface oxides on nickel metal surfaces to the kinetics of oxygen evolution, various transient methods viz. potentiostatic step charging, potentiodynamic linear sweep and galvanostatic discharge methods have been applied. It is shown that higher nickel oxides are reduced in cathodic galvanostatic pulses only to Ni(OH)2 and hydrogen commences to evolve on this latter oxide. A potentiostatic step (anodic) charging method was therefore developed for characterisation of the formation of the surface oxide at nickel in a progressive manner over small intervals of potential. A theoretical treatment for interpretation of results obtained by the step-charging method has been developed. The kinetics of growth of nickel oxides were investigated and it has been observed that the growth kinetics obey a simple logarithmic law. A theoretical formulation of a growth law logarithmic in time has been developed. For the purpose of determining the stoichiometries of the surface oxides formed in the thin film at the metal surface, combined chemical and electrochemical methods were used. For determining micro-quantities of nickel in the thin film oxide layers, a new spectrophotometric method based on the principle of reductive stripping by aq. hydrazine has been developed. Stoichiometries of thin film layers (after allowance for self-discharge effects) are reported as a function of the formation potential. The apparent extent of oxide reduction charge in the thin films, determined electrochemically by a fast galvano-static reduction pulse, and the amount of nickel in the film determined chemically, pass through a maximum at ca. 0.9 V. This is shown to be connected with a change of the oxide layer to a more passive condition. This behaviour is closely connected with the self-passivation effect observed in the kinetics of the anodic oxygen evolution reaction at nickel oxide surfaces. Hysteresis between the charge and discharge processes has been observed both at nickel and silver (similar effects also occur at more noble metals such as platinum, palladium, etc.). This phenomenon has been studied in some detail using potentiodynamic sweep and galvanostatic discharge techniques. It is proposed that hysteresis is an intrinsic thermodynamic effect and is possibly related to the change of state of the system arising from an irreversible rearrangement of the surface oxide during or after its formation.

Woodward's synthesis of sempervirine has been used to prepare 18-methoxysempervirine and 18-benzyloxysempervirine. In each case, the appropriate 4-alkoxyxyxlohexanone was condensed with ethylformate in the presence of sodium methoxide, and then with 2-iodopropane in acetone solution containing potassium carbonate. The resulting 2-isopropoxymethylene-4-alkoxyxyxlohexanone was reacted with the di-lithium salt of harman to give, after acid hydrolysis, the sempervivrine derivative. Attempts to demethylate the methoxysempervirvine or its reduction product 18-methoxyalloyohimbane were unsuccessful. Hydrogenolysis of 18-benzyloxysempervirine in the presence of palladium gave 18-hydroxysempervirine, which on further reduction with Adams' catalyst gave 18-hydroxyalloyohimbane. The sterochemistry of the hydroxyl group was shown in two different ways. The alcohol was oxidized to alloyohimbane-18-one, and the reduction of the ketone with lithium tri tertiary-butoxyaluminum hydride returned the original alcohol. This reducing agent is known to give almost entirely the equatorial isomer. The nuclear magnetic resonsance spectrum of the acetate prepared from the 18-hydroxyalloyohimbane showed that the acetoxy group, and therefore the original hydroxyl group was equatorial. The compound was therefore 18-beta-hydroxyalloyohimbane. The oxidation of 18-beta-hydroxyalloyohimbane with mercuric acetate gave 3-dehydro-18-beta-hydroxyalloyohimbane (isolated as a perchlorate salt) and reduction of thos with zinc and aqueous acetic acid gave 18-hydroxyepialloyohimbane. The sterochemical assignment of this compound was confirmed by the nuclear magnetic spectrum of its' acetate. The 3,4,5-trimethoxybenzoate of 18-beta-epialloyohimbane was prepared for pharmacological testing.

Abstract not available.

A theory of electrostriction of solvent water near ions is developed. The treatment is based on a calculation of the effective pressure which would, in the absence of the field, cause the she change in volume as does the field. It is shown that when the dissolution process is from the crystalline phase, the electrostriction at small ions arises mainly on account of changes of effective volume of the solvent rather than from compression of the ion cavity in the dielectric. The change in solvent volume near ions can be related, using an appropriate molecular model, to the apparent change in the volume of the salt upon dissolution. This treatment avoids the difficulties of previous calculations where use of the Born equation involves an integration over a distance from the ion. Explicit approximate solutions for high-and low-field conditions, and a complete numerical solution for the effective pressure-field and field-volume relations are given. A method for calculation of the compressional entropy associated with hydration of ions is proposed on the basis of the above electrostriction calculations, taking into account dielectric saturation and pressure dependence of dielectric constant. Relations of the electrostatic contributions to the entropy of hydration of ions to corresponding volume changes are investigated and it is shown that the statistical mechanical method of Eley and Evans and the method of Laidler and Pegis, allowing for dielectric saturation, give entropies of hydration that are in better agreement with experimental values. The partial molal volumes V¯ of a series of homologous tetraalkylammonium chlorides, bromides and iodides have been precisely measured by means of a differential buoyancy technique. The extrapolated values of V¯ to infinite dilution give V¯° data which are almost additive for successive homologues and enable the absolute individual partial g. ionic volumes of the halide ions to be estimated by a new principle to an accuracy of about 0.5 ml. (g. ion)-1. The anomalously large negative concentration dependence of V¯ is discussed in terms of mutual salting-in by the large cations and also salting-out due to the anion. Estimates of a and d ln a/dP are also made. Non-electrostatic effects arising from the large differences in size between the cations and the solvent molecules are suggested as one of the reasons for the anomalous activity coefficient and partial molal volume behaviour. It is concluded that the hydrophobic character of these ions exerts a strong structural influence on the solvent water, as indicated in other ways in previous publications. The partial molal volumes of some alkylamine hydrogen halides series have been studied with special reference to the role of solvation in the process of ionisation of methylammonium bases. It is shown that the change in volume associated with the ionisation is almost invariant as the degree of hydrophobic character of the cation is increased. The unexpected behaviour of DeltaS°, DeltaC p and DeltaV¯° is discussed in terms of structural influences upon the solvent by the different species. Partial molal adiabatic compressibility studies have been carried out on the homologous series of tetraalkylammonium bromides and iodides, methylammonium chlorides and methylamines. The extrapolated values of fKs to infinite dilution give f&j0;Ks data which confirm the suspected structure promoting effect of these salts upon solvent water structure; these results complement those obtained from the partial molal volume studies.

The role of 7-(phenylsulfonyl)-bicyclo[4.2.0]octa-1,3,5-triene (benzocyclobutene phenylsulfone (83)) as a synthetic intermediate is investigated. Attempts were made to prepare this compound by several new routes. Cyclization of 1-(chloromethyl),2-(phenylsulfonylmethyl)-benzene ( 127) was attempted with LDA, MeLi, and phase transfer conditions, as well as flash vacuum thermolysis. None of these modifications were successful. The synthesis of phenyl 2-(o-chlorophenyl)ethyl sulfone (80) was approached by a new route in moderate yields by condensation of the anion of methyl phenyl sulfone with o-chloro-benzyl bromide, followed by oxidation. Cyclization of (80) via a benzyne intermediate proved possible with only four equivalents of KNH2. Hindered bases such as 2,2,6,6-tetramethylpiperidide gave intractable tars. The o-quinodimethane intermediate of ( 83) could not be efficiently trapped with maleic anhydride; instead, adducts with toluene and anisole were obtained. A rationale is proposed for this transformation. The anion of (83) was found to be an efficient nucleophile, trapping alkyl bromides, iodides, ketones, and epoxides in high yields. Desulfonylations of the alkylated parent compound were carried out easily and in excellent yields to give the alkyl species. Thermolysis of 7-(phenylsulfonyl)-7-(5'-eta-hexenyl)-1bicyclo[4.2.6]octa-1,3,5-triene (161) resulted in 1,5 hydrogen abstraction to yield styrenes, whereas the desulfonylated species of (161) and (102) were transformed smoothly to tricyclic compounds. Novel approaches to 7-(hydroxy)-bicyclo[4.2.0]octa-1,3,5-triene (benzocyclobutenol (77)) were investigated by intramolecular attack of an aromatic halide on an epoxide via the Grignard or halogen-metal exchange. These attempts did not lead to the desired compound, but instead, gave bromohydrins and olefins.

Theories of magnetism with special reference to the indirect exchange mechanism and ligand field theory are discussed. The magnetic susceptibilities of VF3, MnF3, NiF 2-MgF2, K2NiF4-K2 MgF4, and K3NiF6-K2.8AlF 5.8 were studied range of 90°K to 300°K. The effective magnetic moments of the paramagnetic ions increases as their concentration in the solid solutions decreases. This is explained as being due to the presence of indirect interactions between paramagnetic ions in the pure substance which are decreased by magnetic dilution. It was found that the moments are still dependent upon temperature even at infinite dilution. This behaviour is ascribed to the orbital contribution which is itself temperature dependent. Evidence is adduced for the presence of Ni (III) ion impurities in the NiF2-MgF2 system when it is contaminated with traces of oxide.

It has been demonstrated that the zwitterionic rhodium complex (Rh zw), [Rh(COD)+]BPh4-, is an effective catalyst for the hydroformylation of vinylsilanes. With vinyltrimethylsilane, the branched aldehyde could be obtained as the major aldehyde isomer if the CO:H2 ratio was 1:2 (total pressure = 200 psi). Under these conditions, 20-40% isolated yield was obtained and the low Yield of these reactions was confirmed by experiments performed in deuterated solvents. The hydroformylation of vinyltriethylsilane, on the other hand, gave 66% of the desired aldehydes after 4h. The branched isomer was, however, the minor isomer with B:L selectivities of ca. 35:65. A cationic rhodium complex [Rh(COD)2+]BF 4-, abbreviated as (Rh+), was also found to catalyze the hydroformylation of vinylsilanes, but only in aromatic solvents. With the addition of 1 equivalent of triphenylphosphine, the reaction did proceed in non-aromatic solvents. The addition of PPh3 to the Rhzw catalyzed reactions dramatically improved the yield and selectivity for the linear isomer such that after the addition of only 2 equivalents, the products were formed in 97% yield with a B:L ratio of 7:93. This system is therefore much more sensitive to the effect of phosphines than the neutral complexes reported previously by Takeuchi et al.66 where the addition of 50--100 equivalents of phosphine was required in order to obtain >90% selectivity for the linear isomer. The unique solvent effects observed in the reactions of [Rh(COD) 2+]BF4- were explained by postulating that the aromatic solvent was acting as a ligand for the low-ligated rhodium complex. Furthermore, the activity of the zwitterionic complex in non-aromatic solvents was explained by co-ordination of one of the phenyl rings of the counterion. To gain support for this proposal, the stability of Rhzw under the reaction conditions was examined using high pressure and simple NMR techniques. These experiments led us to conclude that under severe conditions (140°C, 16h), 40% of the counterion is decomposed to benzaldehyde, benzyl alcohol and benzene. The mixture that resulted from this exhaustive treatment was shown to catalyze the hydroformylation of vinyltriethylsilane. However, when the rhodium complex was exposed to the conditions normally employed for carbonylation reactions, (namely 75°C, 3h, 200 psi), less than 15% decomposition to benzaldehyde was observed, and no benzene or benzyl alcohol could be detected. Finally, we prepared a number of arene-rhodium complexes and showed that they catalyzed the hydroformylation of vinyltriethylsilane in non-aromatic solvents. Chiral arene complexes were also prepared in order to test the enantioselectivity of the hydroformylation, but in these reactions, the branched isomer was completely isomerized to the enol silyl ether which did not permit assessment of the enantioselectivity. Other olefins were poor substrates. Styrene and vinyl naphthalene were polymerized under the reaction conditions, and olefin isomerization was problematic in the attempted hydroformylation of aliphatic substrates. The insertion of carbon monoxide into 6-membered ring heterocycles was examined using a variety of 1-alkyl-1,2,3,4-tetrahydroquinoline derivatives. It was found that under forcing conditions using Pd/Cu or Ru/Co complexes, up to 15% of products resulting from insertion of carbon monoxide could be observed. The isolation of these compounds and the determination of their structure was complicated due to the large amounts of metal salts employed, the decomposition of the remaining starting material and the low yields. MS data, however, confirmed that insertion of carbon monoxide had occurred. Finally, we examined the carbonylation of allyl aryl and allyl alkyl sulfides and found that the combination of Pd(OAc)2 and DPPP was effective only if a 1:1 ratio of metal:ligand was employed. Under these conditions, the alpha,beta-unsaturated thioester resulting from carbonylation and isomerization was formed in fair to good yields. Analysis of this compound by 1H NMR indicated that it was 100% trans. When Ru3(CO)12 was employed, the carbonylation could also be effected in lower yields after longer reaction times, and no isomerization of the product was observed. Thus the beta, gamma-unsaturated thioester was obtained from this reaction. The palladium catalyzed carbonylation was shown to proceed through a pi-allyl intermediate since 2-butenyl and 1-(3-butenyl) phenyl sulfide gave the same product. Furthermore, this experiment suggests that the rate determining step was carbonylation and not oxidative addition.

Theories of magnetism with special reference to Ligand field and Kotani's theory are discussed. An investigation of the applicability of Kotani's theory to the complexes of heavy transition elements is described. Magnetic susceptibilities of potassium chloroplatinate, potassium chloroiridate, potassium chloroosmate, potassium bromoosmate, potassium chlororhenate and potassium hydroxy-pentachlorotungstate were measured over a temperature range 90°K to 300°K. It is shown that the complexes, with the exception of potassium chlororhenate, do not obey the Curie-Weiss law. Measurements have been carried out on the paramagnetic salts diluted with isomorphous diamagnetic potassium chloroplatinate and potassium bromoplatinate over a temperature range 90°K to 300°K. It is shown that the magnetic moments of the paramagnetic ions increase as their concentration in the solid solutions decreases. This shows that there is a considerable interaction between paramagnetic ions in crystals of the pure substances and that this interaction is decreased by the inclusion of diamagnetic ions in the crystals, giving a higher value for the magnetic moment. Although pure substances do not follow Kotani's theory, on dissolution in an isomorphous diamagnetic salt there is a trend towards normal behavior and at infinite dilution of the paramagnetic for normal behavior is attained. Thus it has been shown that there is appreciable orbital contribution to the magnetic moment of Ir (IV) ion and that a value of the right order of magnitude for the coupling constant could be calculated from the magnetic susceptibility measurements for ions with dE4 configuration.

addition complexes MX4-2L, where M is Zr or Hf, x is C1 or Br, and L is tetrahydrofuran or tetrahydrothiophene have been prepared. Thermochemical data have been obtained and the results are interpreted. The enthalpies of reaction of MX(c) - 2L-MX4-2L(c) was measured calorimetrically and the values converted to gas phase and correlated in terms of polarizability and steric effects. The compounds MX4 appear to be on the borderline between class a and class b behavior with hafnium showing a very slightly greater tendency toward class b behaviour. The nuclear magnetic resonance spectra have been obtained for these complexes and the internal chemical shifts determined. The order of the increasing internal shift correlates satisfactorily with the order of internal stability of the complexes. Triphenyl phosphine oxide and triphenyl arsine oxide complexes of zirconium tetrachloride and hafnium tetrachloride have been prepared, they are 1:2 addition complexes except ZrCl4-3Ph3AsO which is a 1:3 addition complex. They are insoluble in common solvents tested, hence neither the thermal measurements nor the n. m. r. spectrometry was carried out. Instead, their infrared spectra were studied with those of corresponding niobium complexes which have also been prepared as 1:2 addition compounds. The analyses of the shifts of the P-O and As-O stretching frequencies confirm the relative hardness of zirconium(IV) chloride and hafnium(IV) chloride as Lewis acids, hence the relative tendency toward class b behaviour thermochemically observed for zirconium and hafnium.