Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15039号 / 工博第3188号 / 新制||工||1479(附属図書館) / 27500 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 濵地 格, 教授 森 泰生, 教授 白川 昌宏 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16886号 / 工博第3607号 / 新制||工||1545(附属図書館) / 29561 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 濵地 格, 教授 森 泰生, 教授 白川 昌宏 / 学位規則第4条第1項該当

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17162号 / 工博第3652号 / 新制||工||1555(附属図書館) / 29901 / 京都大学大学院工学研究科分子工学専攻 / (主査）教授 佐藤 啓文, 教授 横尾 俊信, 教授 梶 弘典 / 学位規則第4条第1項該当

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18823号 / 理博第4081号 / 新制||理||1587(附属図書館) / 31774 / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 時任 宣博, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20200号 / 理博第4285号 / 新制||理||1615(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 大須賀 篤弘, 教授 依光 英樹, 教授 丸岡 啓二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

<p> Studies of the bonding and reactivity of transition metal complexes constitute a large fraction of current research in inorganic chemistry. The present thesis describes three contributions to this area. In each case, Nuclear Magnetic Resonance studies of paramagnetic complexes are involved. An introductory chapter briefly reviews some of the pertinent background. In the second chapter the NMR theory which forms the basis for interpreting the experimental results is developed. </p> <p> The major topic of the thesis is concerned with the effect of ligand substitution on the charge distribution of a transition metal complex. Interest in this topic is aroused by the many reports that the reactivity of transition metal complexes can be considerably affected by modification of the ligands. This is particularly notable in the area of homogeneous catalysis. It seemed possible that NMR studies of paramagnetic complexes might provide a probe for these effects. With this objective in view the NMR spectra of a series of trisβ diketonato V(III) complexes have been examined. It was found that substituent changes on one ligand brought about very large (several thousand Hz) changes in the isotropic shifts of protons or fluorine atoms located on another ligand. A rather complete study has been carried out on the series of complexes formed by systematically substituting CF₃ groups for CH₃ groups on tris-acetyl-acetonato V(III). Ninety-nine of the possible one hundred different ¹H and ¹⁹F resonances in this system have been observed and identified. This relatively large body of data enabled us to attempt an empirical analysis of the results in terms of changes in the charge distribution in the complex brought about by substitution. Arguments are presented to show that the isotropic shifts arise predominantly from contact interactions. It was found necessary to introduce two terms in the empirical equations describing the shifts. The first represents changes in the distribution of the unpaired electrons in the Vanadium(III) d orbitals brought about by modification of the crystal field potential produced by the ligands. The second represents variations in the ability of a ligand to accept electron density by metal to ligand charge transfer due to inductive effect of the substituent. Two term empirical equations of this type reproduce the observed shifts to within 2%. The significance of the parameters obtained from this analysis is discussed in some detail. These studies have been extended to include several other substituted β-diketone ligands. A similar analysis has proved feasible and a consistent pattern of substituent parameters is obtained. </p> <p> The second topic considered is closely related to the above study. The interest in this case was in the possible importance of dipolar shifts in determining the isotropic shifts of mixed chelates. A series of six coordinated Co(II) complexes wa.a chosen for this purpose. These compounds are known to possess considerable magnetic anisotropy and dipolar shifts are therefore to be expected. However analysis of the results reveals that the substituent shifts are very similar to those for the V(III) compounds. It appears that the mode of transmission of substituent effects proposed may be quite general for many transition metal complexes. </p> <p> The third topic involved in this thesis concerns the structure of the second coordination sphere of transition metal complexes. The participation of various solvents in the second coordination sphere of tris-pyrazolylborate Co(II) has been investigated. Equilibrium constants relative to carbon tetrachloride as a second sphere ligand have been obtained. The ability of a solvent to participate in the second sphere depends predominantly on its dipole moment and it is concluded that Van der Waals forces are responsible for outer sphere binding. </p> / Thesis / Doctor of Philosophy (PhD)

[Formulae and special characters can only be approximated here. Please see the pdf version of the Abstract for an accurate reproduction.] The kinetics for outer-sphere electron transfer between a series of cobalt(II) poly-aza cage ligand complexes and the iron(III) sarcophagine-type hexa-aza cage complex, [Fe(sar)]3+ (sar = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane), in aqueous solution have been investigated and the Marcus correlation is used to deduce the electron self-exchange rate constant for the [Fe(sar)]3+/2+ couple from these cross-reactions. The deduced electron self-exchange rate constant is in relatively good agreement with the experimentally determined rate constant (k ex calc = 4 ´ 10 5 M -1 s -1 ; k ex obs = 8 ´ 10 5 M -1 s -1 ). The successful application of the Marcus correlation to the electron transfer reactions of the Fe cage complex is consistent with the trend for the Co, Mn, Ni and Ru cage complexes which all follow the pattern of outer-sphere electron transfer reactivity expected from the Marcus-Hush formalism. A comparison of predictions based on the Marcus correlation with the experimentally determined kinetics of an extended series of cross reactions involving cobalt cage complexes with low-spin-high-spin cobalt(III)/(II) couples shows that electron transfer reactions involving large spin changes at the metal centre are not necessarily anomalous in the context of the adiabatic Marcus-Hush formalism. The results of this study also show that for suitable systems, the Marcus correlation can be used to reliably calculate the rates of outer-sphere electron transfer cross-reactions, with reaction free-energy changes spanning the range -6 to -41 kJ mol -1 and many different combinations of initial electronic configurations. Together, these results provide a coherent and internally consistent set of experimental data in support of the Marcus-Hush formalism for outer-sphere electron transfer. The results with the caged metal-ion systems also highlight the special nature of the mechanism of electron transfer in reactions of metal-aqua ions. ¶ A new range of symmetrically disubstituted hexa-aza sarcophagine-type cage ligand complexes are prepared in this study by the base-catalysed co-condensation of formaldehyde and a-methylene aliphatic aldehydes with cobalt(III) tris(1,2-diamine) precursors in acetonitrile solution. Encapsulation reactions based on the condensation of the weak carbon di-acids propanal and decanal with formaldehyde and the cobalt(III) tris(1,2-diamine) precursors, [Co(en)3 ] 3+ (en = 1,2-ethanediamine) and D-lel3 -[Co((R, R)-chxn)3 ] 3+ (chxn = 1,2-cyclohexanediamine), yield unsaturated cobalt(III) cage complexes with an endo-cyclic imine function in each cap. The Co III -coordinated endo-cyclic imine units of the cage ligands are reactive electrophiles that are readily reduced by the BH4 - ion to give the corresponding symmetrically di-substituted hexaamine macrobicyclic cage ligands. The nitromethane carbanion is also shown to add at the endo-cyclic imine function to yield a novel nitromethylated cage ligand complex. The latter reaction introduces a new method for the regioselective functionalisation of cage ligands at sites removed from the more commonly substituted bridgehead positions. The capping of cobalt(III) tris(1,2-diamine)-type complexes with weak CH-acids developed in this study introduces a new and more direct route to symmetrically di-substituted cage ligand complexes. ¶ A new range of cobalt(III) surfactant cage complexes, with linear octyl, dodecyl and hexadecyl hydrocarbon chains built directly into the bridgehead structure of the cage ligand, have been prepared by the base catalysed co-condensation of formaldehyde and long chain aliphatic aldehydes with the tripodal cobalt(III) hexaamine complex, [Co(sen)]3+ (sen = 4,4',4''-ethylidynetris(3-azabutan-1-amine)), in acetonitrile solution. Chiral surfactant cage complexes are obtained by capping reactions beginning with the optically pure L-[Co(sen)]3+ precursor complex. The cobalt(III) cage complexes with octyl to hexadecyl substituents are surface active and reduce the surface tension of water to levels approaching those of organic solvents. The dodecyl substituted cage complex forms micelles in aqueous solution when the concentration of cage complex is > 1 ´ 10 -3 mol dm -3 at 25 °C. The cobalt(III) cage head-group of these surfactants undergoes an electrochemically reversible one-electron reduction to the corresponding cobalt(II) cage complex. The reduction potential of the surfactant head group can be tuned to more positive potentials by replacing the bridgehead hydrocarbon chain substituent with an ether linked hydrocarbon chain. The cobalt(III) surfactant-cage complexes are biologically active and are lethal to the tapeworm Hymenolepis diminuta, and the vaginal parasites, Trichomonas vaginalis and Tritrichomonas foetus. The surfactant cage complexes also cause lysis in red-blood cell membranes at concentrations as low 10 -5 mol dm -3 . Their biological activity is linked to the high head-group charge (3+) and size which cause distortions in biological membranes when the membrane is treated with these molecules. The combination of the chemically reversible outer-sphere redox properties of the cobalt cage head-groups and the chirality of the head group introduces a new and possibly unique series of chiral surfactant coordination complexes which are also redox active. ¶ The chiral carboxylic-acid ionophore, lasalocid A, has been used to promote the selective supramolecular transport and extraction of cobalt(III) hexa-aza cage cations and related tripodal cobalt(III) complexes. The conjugate base anion of lasalocid A forms stoichiometric outer-sphere complexes with the cobalt(III) cage and tripod complexes. These outer-sphere complexes are highly lipophilic and partition strongly from water into a chloroform phase. The extraction of the dissymmetric cobalt(III) complexes by the chiral polyether anion is enantioselective for many systems and results in the partial resolution of initially racemic complexes in the aqueous phase. A strong structural preference was demonstrated by the ionophore for symmetrically disubstituted cobalt(III) hexa-aza cage cations with a D-absolute configuration of the ligand about the metal-ion and an R configuration of the coordinated secondary amine N-H groups. The lasalocid A anion was also shown to promote the transport of the complexes, intact, across a chloroform bulk-liquid membrane against an NH4 + concentration gradient. The transport of the cobalt(III) complexes was also enantioselective and resulted in partial resolution of the initially racemic aqueous phase. The most efficiently transported enantiomer of each complex was also the most efficiently extracted isomer in all systems examined, consistent with a transport process limited by interfacial diffusion. The magnitude of the enantiomer separation obtained in some systems was sufficient to indicate that lasalocid A mediated extraction and transport may become a practical method for the resolution of particular types of kinetically-inert chiral metal-amine complexes.

Metal complex dyes are a problematic group of substances, present in the negatively charged anion form in mixed industrial wastewater that should be removed. Therefore, a complete removal of these hazardous dyes from wastewaters is necessary to prevent them from release into the environment. Adsorption on activated carbon of dyes has been investigated widely. However some disadvantages using activated carbon in practice were observed, e.g. high regeneration costs and production of fines due to the brittle nature. Since their adsorption capacities, mechanical strength, and other properties need further improvement for wider application, the polymeric sorbents are still under development as a potential alternative to activated carbons. The main aim of the present work was to investigate absorption regularity metal complex Lanasyl Navy M-DNL and Acid Blue 249 (copper (II) phthalocyanine) dyes on synthetic ion exchangers under static conditions and evaluate facility of ion exchangers to removal dyes from wastewaters by dynamic conditions. Screening with chromium-complex dye (acid brown NKM, Lanasyn Navy M-DNL) solutions wide range sorbents, according to the physical chemical characteristics of sorbents and established dye removal parameters (sorption capacity, distribution coefficient and sorbent regeneration) has shown that the polyacrylic, gel type, weakly basic anion exchanger Purolite A 847 (A 845); polystyrene, macroporous, strongly basic anion exchanger Purolite A 500 PS... [to full text] / Pagrindinis aplinkosauginės politikos bruožas yra taršos metalo dažikliais mažinimas gamybos metu ir efektyvių šalinimo iš nuotekų metodų paieška. Regeneruojami, mechaniškai atsparūs ir nekenksmingi gamtai polimeriniai sorbentai naudojami dažikliams valyti yra pranašesni už plačiai paplitusias aktyvintąsias anglis. Ištyrus polimerinių sorbentų sorbcines ir regeneracines savybes, nustačius palankias darbines sąlygas, sorbentai gali būti pritaikomi nuotekų valymui, o išvalytas vanduo grąžinamas atgal į gamybinius procesus. Tokiu būdu, vandens ištekliai gali būti apsaugoti nuo taršos sunkiaisiais metalais ir organiniais junginiais, sumažinti gamybos kaštai, nes regeneruoti sorbentai naudojami pakartotinai. Šiame darbe tiriama metalo kompleksinių dažiklių Navy M-DNL (1:2 chromo monoazo kompleksas) (Navy) ir Acid Blue 249 (Vario (II) ftalocianino tetrasulforūgšties tetranatrio druska) (CuPc) sorbcijos sintetiniais jonitais dėsningumus statinėmis sąlygomis ir įvertinti jonitų galimybes valyti nuotekas nuo dažiklių dinaminėmis sąlygomis. Geriausiai iš vandeninių tirpalų šalinantys dažiklius sorbentai atrinkti pagal geriausią sorbcinė gebą ir regeneraciją, dažiklio pasiskirstymo tirpale koeficientą yra: silpnai baziniai anijonitai Purolite A 847 (A 845), stipriai bazinis anijonitas Purolite A 500PS, nejoninis makrotinklinis sorbentas Macronet MN 200. Statinėmis sąlygomis nustatyta dažiklių (Navy ir CuPc) sorbcijai palankiausia terpė (pH 2) ir temperatūra atitinkamai dažikliui Navy... [toliau žr. visą tekstą]

Pagrindinis aplinkosauginės politikos bruožas yra taršos metalo dažikliais mažinimas gamybos metu ir efektyvių šalinimo iš nuotekų metodų paieška. Regeneruojami, mechaniškai atsparūs ir nekenksmingi gamtai polimeriniai sorbentai naudojami dažikliams valyti yra pranašesni už plačiai paplitusias aktyvintąsias anglis. Ištyrus polimerinių sorbentų sorbcines ir regeneracines savybes, nustačius palankias darbines sąlygas, sorbentai gali būti pritaikomi nuotekų valymui, o išvalytas vanduo grąžinamas atgal į gamybinius procesus. Tokiu būdu, vandens ištekliai gali būti apsaugoti nuo taršos sunkiaisiais metalais ir organiniais junginiais, sumažinti gamybos kaštai, nes regeneruoti sorbentai naudojami pakartotinai. Šiame darbe tiriama metalo kompleksinių dažiklių Navy M-DNL (1:2 chromo monoazo kompleksas) (Navy) ir Acid Blue 249 (Vario (II) ftalocianino tetrasulforūgšties tetranatrio druska) (CuPc) sorbcijos sintetiniais jonitais dėsningumus statinėmis sąlygomis ir įvertinti jonitų galimybes valyti nuotekas nuo dažiklių dinaminėmis sąlygomis. Geriausiai iš vandeninių tirpalų šalinantys dažiklius sorbentai atrinkti pagal geriausią sorbcinė gebą ir regeneraciją, dažiklio pasiskirstymo tirpale koeficientą yra: silpnai baziniai anijonitai Purolite A 847 (A 845), stipriai bazinis anijonitas Purolite A 500PS, nejoninis makrotinklinis sorbentas Macronet MN 200. Statinėmis sąlygomis nustatyta dažiklių (Navy ir CuPc) sorbcijai palankiausia terpė (pH 2) ir temperatūra atitinkamai dažikliui Navy... [toliau žr. visą tekstą] / Metal complex dyes are a problematic group of substances, present in the negatively charged anion form in mixed industrial wastewater that should be removed. Therefore, a complete removal of these hazardous dyes from wastewaters is necessary to prevent them from release into the environment. Adsorption on activated carbon of dyes has been investigated widely. However some disadvantages using activated carbon in practice were observed, e.g. high regeneration costs and production of fines due to the brittle nature. Since their adsorption capacities, mechanical strength, and other properties need further improvement for wider application, the polymeric sorbents are still under development as a potential alternative to activated carbons. The main aim of the present work was to investigate absorption regularity metal complex Lanasyl Navy M-DNL and Acid Blue 249 (copper (II) phthalocyanine) dyes on synthetic ion exchangers under static conditions and evaluate facility of ion exchangers to removal dyes from wastewaters by dynamic conditions. Screening with chromium-complex dye (acid brown NKM, Lanasyn Navy M-DNL) solutions wide range sorbents, according to the physical chemical characteristics of sorbents and established dye removal parameters (sorption capacity, distribution coefficient and sorbent regeneration) has shown that the polyacrylic, gel type, weakly basic anion exchanger Purolite A 847 (A 845); polystyrene, macroporous, strongly basic anion exchanger Purolite A 500 PS... [to full text]

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23715号 / 理博第4805号 / 新制||理||1688(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM