Download Container Molecules and Their Guests by Donald J. Cram, Jane M. Cram PDF
By Donald J. Cram, Jane M. Cram
This quantity covers the evolution of host-guest complexation chemistry within the minds and arms of Nobel Prize winner Donald Cram and his co-workers at UCLA over the interval from 1970 to 1994. It offers with the elemental rules and ambitions that govern this quickly constructing topic and illustrates the emergence of the sector of biomimetic chemistry. The ebook demonstrates how a couple of recommendations, resembling molecular modelling, synthesis, crystal constitution, NMR resolution constitution and mass spectral constitution determinations should be mixed to advance a brand new department of natural chemistry. It discusses the chemistry of thoroughly new households of complexes - the carceplexes, hemicarceplexes and velcraplexes - and studies the makes use of of the interiors of hemicarceplexes as a brand new part for accomplishing chemical reactions and for safeguarding risky species.
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Extra resources for Container Molecules and Their Guests
Example text
When the numbers of anisyl groups were increased to eight as in 50, the two CH3 groups of the OCH3 moieties at 12 and 6 o'clock turned inward to fill the cavity, as shown by the crystal structure 50a? When complexed with Cs+, as in 51, these methyl groups turned outward, as shown by its crystal structure 52. J. A. P. M. Lein, I. B. F. N. Trueblood, J. Am. Chem. ,1987,109, 7068. 0 kcal mol-’. Ofthese ions only Cs+ is large enough to contact all of the oxygens at the same time, and it shows the strongest binding.
This idea is implicit in all host-guest studies, but is so important that it deserves to be put in explicit form and given a name. We have called it the ‘principle of complementarity’, and have stated it as follows: to complex, hosts must have binding sites which can simultaneously contact and attract the binding sites of guests without generating internal strains or strong non-bonded repulsions. J. Cram, ‘From Design to Discovery’, American Chemical Society, Washington, DC, 1990, p. 91. 000 >lo9 R b+/Css 900 Na+/Li+ 440 K+/Na+ 11,000 K+/Na+ 440 Rb+/Cs+ 58,000 co..
Rr-base at tractions, metal-ion ligation, induced dipole4ipole effects, and van der Waals attractions. Usually each contact involves c 1 kcal mol-’ of free energy, two orders of magnitude less than the energies of covalent bonds. Complexation can compete with solvation only when many contact sites are collected in the same molecule and can act simultaneously, so that binding forces at each site are additive. This idea is implicit in all host-guest studies, but is so important that it deserves to be put in explicit form and given a name.