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Download e-book for kindle: Container Molecules and Their Guests by Donald J. Cram, Jane M. Cram

By Donald J. Cram, Jane M. Cram

ISBN-10: 0854045074

ISBN-13: 9780854045075

This quantity covers the evolution of host-guest complexation chemistry within the minds and fingers of Nobel Prize winner Donald Cram and his co-workers at UCLA over the interval from 1970 to 1994. It bargains with the elemental rules and ambitions that govern this swiftly constructing topic and illustrates the emergence of the sector of biomimetic chemistry. The booklet demonstrates how a couple of innovations, akin to molecular modelling, synthesis, crystal constitution, NMR answer constitution and mass spectral constitution determinations should be mixed to strengthen a brand new department of natural chemistry. It discusses the chemistry of thoroughly new households of complexes - the carceplexes, hemicarceplexes and velcraplexes - and reports the makes use of of the interiors of hemicarceplexes as a brand new section for accomplishing chemical reactions and for shielding volatile species.

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The bromide ions are arranged around the equator of the macrocycle as shown in 64 and 65. 3A apart. Our expectation that the bromide ions would occupy the cavity of the cyanospherand was not fulfilled. K. B. F. J. Cram, J. Am. Chem. , 1989, 111,8662. 0 kcal mol - At the concentrations employed (10 - M for host and guest), . vapor-pressure osmometry (46 "C) demonstrated the complex to be composed of one host and one guest molecule. 1 kcal mol- I . These values proved to be higher by > 4 to > 8 kcal mol-' than those found for the open-chain values were all below the counterpart B ~ ( ~ - C H ~ C ~ H ~ C N whose ) ~ B I-- AGO , detectable level ( < 6 kcal mol-I).

An examination of the structures of naturally occurring alkali metal ion binders, ionophores, indicates them to be rich in heteroatoms embedded in fiveor six-membered ring systems. Often these systems are incorporated into macrorings which provide for an orderly spacing of oxygen or nitrogen ligating sites whose electron pairs can face inward in low energy conformations. The numbers of their conformations are severely limited by the ring systems and by an artful use of steric effects. Chemical evolution of these ionophores has provided a series of ion-specific compounds preorganized to possess 6-10 ligating sites which sequentially replace water of solvation by conformational reorganization to give nesting or capsular complexes.

O 2' 22 M. Tagaki, H. Nakamura, and K. Ueno, Anal. , 1977, 10, 1 1 15. P. Dix and F. Vogtle, Angew. , Znt. Ed. , 1978, 17, 857; H-G. Lohr and F. Vogtle, Acc. Chem. , 1985, 18, 65. T. Kaneda, K. Sugihara, H. Kamiya, and S. , 1981, 22,4407. Spherands, Spheraplexes, and Their Relatives 47 67 k N b.. NO2 NO2 72 73 and Na+ to form 72 and 73, respectively. The pK, values of 71, 72, and 73 are 13, 6, and 7, respectively. The presence of the Li+ in 72 increases the acidity of the phenolic proton by 7 powers of 10, and the Na+ in 73 by 6 powers of 10.

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Container Molecules and Their Guests by Donald J. Cram, Jane M. Cram

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