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An Equilibrium and Kinetic Study of Cryptand, Lariat Ether And ao'\ q AI\ or EQUILIBRIUM AND KINETIC STUDY OF CRYPTAND, LARIAT ETHER AND FLUORESCENT ZINC(II) COMPLEXES by Theo Rodopoulos B.Sc.(Hons.) (Adelaide) This thesis is presented for the degree of Doctor of Philosophy Department of Chemistry University of Adelaide September,1993 \n,^n À".1 r{au¡ (iÐ C ontents Contents ll Abstract v vll Acknowledgements Abbreviations. ix Chapter 1: Cryptands, Lariat Ethers and their Complexes............1 1.1 General Introduction......... ........1 1.2 Structural Aspects of Cryptates and Lanat Ether Complexes...8 1.3 Applications of Macrocyclic Chemistry....... .........20 References 22 Chapter 2: Equilibrium Studies of Cryptates and Lariat Ether Complexes 28 2.1 Introduction 28 2.2 Stability Constant Determination Techniques........... 37 2.2.1 The Potentiometric Titration Technique......... 31 2.2.2 The pH-Metric Titration Technique .49 2.3 Results and Discussion.... .52 2.3.L Complexation of Monovalent Metal Ions by the Cryptands CZLI and C21C5 in Trialkyl Phosphate So1vents...................52 2.3.2 Complexation of Alkali and Ag(I) Metal Ions by the Lariat Ethers BHE-C2l and BHE-C22 in Non-Aqueous Solvents.....60 2.3.3 Protonation of BHE-C2l and BHE-Czz in Aqueous Solution 69 2.3.4 Complexation of Divalent Metal Ions by the Lariat Ethers BHE-C21 and BHE -C22 in Aqueous Solution........... ............1 I References 77 Chapter 3: Metal Ion Exchange on Cryptates and Lariat Ether C omplexes 82 3.1 Introduction 82 3.2 Results and Discussion.... 88 3.2.L Exchange Kinetics of Na+ on [Na.CZIt1+ 88 3.2.2 Exchange Kinetics of Li+ on [Li.C2lCs]+ 92 3.2.3 Qualitative Study of the Exchange Kinetics for [Li.C2l1]+ and [Na.C2 1 Cs]+ in Trialkyl Phosphate So1vents............ ......92 (iii) 3.2.4 General Conclusions for the [M.C211]+ and [M-C21Cs]+ Systems in Various SoIvents............ 97 3 .2.5 Exchange Kinetics of Na+ on [Na.BHE-C21]+ in Acetonitrile and INa.BHE -C221+ in Methanol. 103 3 .2.6 Exchange Kinetics of Li+ on [Li.BHE-C211+ itt N,N-Dimethylformamide and Methanol. r07 3.2.7 Qualitative Study of the Exchange Kinetics for [M.BHE- CZtl+ and [M.B HE -C22)+ in Selected Solvents "'' " 1 07 3.2.8 General Conclusions for the [M.BHE-C211+ *¿ [M.BHE- C2Z1+ Systems in Various Solvents...................... 1 I 0 References ..ltl Chapter 4: The Study of a Fluorescent Sulfonamidoquinoline Probe for Zinc(II). L22 4.L Introduction r22 4.2 Complexation Properties of MTS-Q44..... r26 4.2.L Protonation and Stability Constant Determination. r26 4.2.2 Results and Discussion 127 4.3 Spectral Properties of MTS-Q44.......... 135 4.3.L Principles of Fluorescence Spectroscopy 135 4.3.2 Results and Discussion........... r37 4.4 Reaction Kinetics for IZn.MTS-QAA] and IZn.MTS-QAR21z t44 4.4.L Stopped-flow Fluorescence Spectroscopy. ....------.144 4.4.2 Ligand Substitution Mechanisms.... .....I45 4 .4.3 Results and Discussion.... .......150 4.4.3.L Acid Catalysed Decomplexation of IZn.MTS-QAA]...--.......150 4 .4.3.2 Acid Catalysed Decomplexation of IZn.MTS-QAAù2-.---..-.155 4.4.3.3 Formation of [Zn.MTS-QAA]... 159 References 168 Chapter 5: Experimental.... 17I 5.1 Cryptands and Lariat Ethers.... r71. 5.1.1 Origin and Purification of Materials......... t7l 5 .1.2 Synthesis r72 5 .L.2.r Preparation of CZlCs... 172 5 .L.2.2 Preparation of BHE -C22 t74 5 .1.2.3 Preparation of BHE-C2l 174 5.1.3 Stability Constant Measurements........ n5 5.1.3.1 Potentiometric Titrations. 175 (iv) 5 .1.3.2 pH-Metric Titrations I7l 5.1.4 7Li and 23Na Variable Temperature NMR Spectroscopy..... 178 5.2 2- Methyl-8 -p-toluenesulfonamido -6 -qu inolyloxyacetic 180 5 .2.1 Origin and Purification of Materials...... 180 5 .2.2 pH-Metric Titrations........ 180 5 .2.3 Ultraviolet-Visible Spectroscopy..... t82 5 .2.4 Fluorescence Spectroscopy. 183 5.2.5 Fluorescence Stopped-flow Kinetics. 183 References 186 Chapter 6: NMR Data Analysis 188 6.1 NMR Analysis of Two-Site Chemical Exchange....... 188 6.1.1 7Li and 23Na NMR Specrroscopy......... 188 6.I.2 Two-Site Chemical Exchange ..188 6.2 Two-Site Lineshape Analysis. r97 6.3 Activation Parameter Determination r99 References 200 Publications 202 (v) Abstract In the first part of this work the complexation of M+ = Li+, Na+, Ag+ and Tl+ by the cryptands 4,7,13,18-tetraoxa- l, 1 O-di azabicy clo [8. 5.5 ]eicosane (CZII) and 4,7,L3-trioxa-l ,10-diazabicycto[8.5.5]eicosane (C2lCs) to form the cryptates [M.C2111+ und [M.C21C5]+ was studied in a variety of trialkyl phosphate solvents by potentiometric titration and 7Li and 23Na NMR spectroscopy. This study enabled the effect of variation in donor atoms and the influence of solvent molecular size on cryptate st¿bility and lability to be investigated. The decomplexation kinetic parameters for [Na.C211]* in trimethyl phosphate, triethyl phosphate and tri-n-butyl phosphate, and for tli.C2lcsl+ in trimethyl phosphate and triethyl phosphate were derived by complete two-site lineshape analysis of the coalescing 23Na or 7Li resonances. The dominant mechanism for metal ion exchange in these systems involved a monomolecular decomplexation of the metal ion. Metal ion exchange on ÍLi.CZIll+ and [Na.C21C5]+ was in the very slow and very fast extreme of the NMR time scale, respectively, in trimethyl phosphate and triethyl phosphate. The equilibrium and kinetic data are compared with data obtained in other solvents and discussed in terms of the metal ion and cryptand intramolecular cavity size, metal ion-cryptand bonding interactions, solvent interactions and the solid state crystal structures of the cryptates. Furthermore, the complexation characteristics of the pendant armed bibracchial lariat ethers 1,7-bis(2-hydroxyethyl)-4,10,13-trioxa-L,'l' dlazacyclopentadecane (BHE-C2l) and 1,10-bis(2-hydroxyethyl)- ,7,13,16- tetraoxa-1,lO-diazacyclooctadecane (BHE-C22) with alkali, alkaline-earth, transition and heavy metal cations in aqueous solution and several non- aqueous solvents was investigated by potentiometric and pH-metric titration. The results are discussed in conjunction with data from related structures, such as the bibracchial lariat ethers BME-C2l and BME-C22, the diaza crown ethers CZl and C22, and the cryptands C221, C222, C22C5 and C22Cg. The kinetics of decomplexation of [Na.BHE-C21]+ in acetonitrile, INa.BHE -CZZ1+ in methanol and [Li.BHE-C2t1+ in methanol and N,N- dimethylformamide were measured by 23¡u and 7Li variable temperature NMR. A monomolecular exchange mechanism was found to be in operation in each of the systems lineshaped. The kinetic data are compared with data from related systems. (vi) In the second part of this work the viability of the fluorophore 2-methyl-8- p-toluenesulfonamido-6-quinolyloxyacetic acid (MTS-QAA) to behave as a ZnZ+ specific probe and quantify intracellular ZnZ+ levels was investigated. The spectral and kinetic properties of MTS-QAA with Zn2* were studied as well as its complexation properties with ZnZ+, Co2+, Ni2+, Cu2+, Cd2+ and Mg2+ in a 50Vo ethanol/5O%o water solvent mixture. MTS-QAA formed two stable Zn2+ complexes, namely IZn.MTS-QAA] and IZn.MTS-QAAzl2-, which would complicate the quantification of Znz+ levels in biological systems. Tlne ZnL+-free and Zn2+-bound forms of MTS-QAA were seen to fluoresce at the same wavelength. In addition, a MTS-QAA molecule in the IZn.MTS-QAA] complex form was found to fluoresce much more strongly than a MTS-QAA molecule in the uncomplexed form and more strongly than a MTS-QAA molecule in the [Zn.MTS-QAAZ)2- complex form. The kinetic study of the ZnZ+-MTS-QAA complexes in 507o ethanoV5ÙVo water provided an insight into their complexation and decomplexation mechanisms. Results from the study of the formation of IZn.MTS-QAAI suggested that ring closure or formation of the second coordinate bond was the rate determining step. (vii) Statement This work contains no material which has been accepted for the award of any other degree or diploma in any university or other tertiary institution and, to the best of my knowledge and belief, contains no material previously published or written by another person, except where due reference has been made in the text. I give consent to this copy of my thesis, when deposited in the University Library, being available for loan and photocopying. SIGNED: DATE: ra/ 2/ u Theo Rodopoulos (viii) Acknowledgements I wish to extend my thanks to my supervisor, Prof. S.F. Lincoln for his help, guidance and encouragement throughout the course of this work. I would like to thank Dr. P.-4. Pittet for his invaluable help with the fluorescence work and Dr. I. Mahadevan for supplying the sulfonamidoquinoline ligand. I would also like to thank my fellow research students for their helpful discussions and suggestions, their frienship and the many good time shared, especially -y fiancee Mary Manikas and Rob Jones. I gratefully acknowledge the fînancial support of an Australian Postgraduate Research Award for the period of my candidature. Finally, I would like to express my gratitude to my family for their encouragement, support, patience and understanding. (ix) Abbreviations The following abbreviations have been used in this study: 18-crown-6 1,4,7,10,13, I 6-hexaoctadecane CZL 4 ,7 ,13 -trioxa- 1 , 1 0-diazacyclopentadecane c22 4,7,13, 1 6 -te traoxa- 1, I 0- diazacy cto octadecane CzLI 4,7,L3,18-tetraoxa- 1, I 0-diazabicyclo [8. 5. 5] eicosane C2ICs 4,7,L3 -tnoxa- 1, 1 O-diazabicyclo [8.5.5 ] eicosane C22T 4,'l,l3,L 6,2L -pentaoxa- 1, 1 O-diazabicyclo [8.8.
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