cr00068a003 - Chem Rev 1985,8 5 271-339 27 1 Thermodynamic...

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Chem. Rev. 1985, 85, 271-339 27 1 Thermodynamic and Kinetic Data for Cation-Macrocycle Interactiont REED M. IZATT,’ JERALD S. BRADSHAW, STEVEN A. NIELSEN, JOHN D. LAMB, and JAMES J. CHRISTENSEN Departments of Chemistry and Chemical Engineering and Thermochemical Institute, Brigham Young University, Provo, Utah 84602 DEBABRATA SEN Department of Chemistry, Indian Institute of Technology, Kharagpur, India Received December 3, 1984 (Revised Manuscript Received May 10, 1985) Confenfs I. Introduction I I. Thermodynamics of Cation-Macrocycle Interaction A. Cation-Coronand Complexation 1. Relative Cation and Ligand Cavity Sizes 2. Number and Stereochemical Arrangement of Ligand Binding Sites 3. Substitution on the Macrocycle Ring 4. Solvent Effects 5. Catioh-Polyamine Complexation 6. Cation-Polythioether Complexation 7. Cation-Mixed Donor Atom Macrocycle Complexation B. Cation-Cryptand Complexation 1. Relative Cation/Anion and Ligand Cavity Sizes Number and Stereochemical Arrangement of Ligand Binding Sites Substitution on the Macrocycle Ring 4. Solvent Effects C. Cation-Spherand Complexation D. Anion Effect E. Macrocyclic Effect 1. Tetraamines Polythia Ethers Cyclic Polyethers Mixed Donor Atom Macrocycles F. Cryptate Effect A. Crown Ethers B. Cryptands C. Macrocycles Containing Nitrogen Donor Atoms D. Macrocycles Containing Oxygen and Nitrogen Donor Atoms E. Kinetic Data for Reactions Involving Metal-Macrocycle Complexes I I Kinetics of Cation-Macrocycle Interaction IV. References 27 1 273 275 318 319 320 32 1 1 1 1 322 323 324 325 333 334 335 Introduction The that cations and anions form stable complexes with macrocyclic polyethers and polyamines Contribution No. 273 from the Thermochemical Institute. has opened the door to several broad and fruitful areas of chemical investigation. The interest in these mac- rocycles was stimulated when it was found that certain of them formed stable complexes with alkali and alka- line earth metal ions and that preferential cation com- plexation resulted when the relative sizes of the cation and ligand cavity were mat~hed.~ In addition, these synthetic ligands are similar in their structures and reactions to many naturally occurring compounds of the macrocyclic type which are known to exhibit selective cation c~mplexation.~ A number of macrocyclic com- pounds having more than one cyclic ring and having donor atoms such as sulfur and phosphorus in place of the well-known oxygen, nitrogen, and oxygen-nitrogen combinations have been synthesizede6 The synthesis and subsequent study of a large number of these ligands have presented a challenge in interpreting the cation and anion binding data in terms of the observed se- lectivities and solvation characteristics of the ligands under various experimental conditions. Chiral deriva- tives of macrocycles can distinguish between enan- tiomers of optically active organic cation^^-^ and have been used in their separation.8 Macrocyclic ligands have been used successfully for diverse processes such as separation of ions by transport through artificial and
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cr00068a003 - Chem Rev 1985,8 5 271-339 27 1 Thermodynamic...

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