The Chemistry of Organolithium Compounds. by Zvi Rappoport, Ilan Marek

By Zvi Rappoport, Ilan Marek

Patai sequence: The Chemistry of practical Groups

a sequence of complex treatises based by means of Professor Saul Patai and below the overall editorship of Professor Zvi Rappoport

The Patai sequence publishes entire stories on all points of particular sensible teams. every one quantity comprises notable surveys on theoretical and computational points, NMR, MS, different spectroscopical tools and analytical chemistry, structural facets, thermochemistry, photochemistry, artificial methods and techniques, man made makes use of and functions in chemical and pharmaceutical industries, organic, biochemical and environmental aspects.

up to now, over a hundred volumes were released within the series.

lately released Titles

* The chemistry of the Cyclopropyl crew (Volume 2)
* The chemistry of the Hydrazo Azo and Azozy teams (Volume 2, 2 parts)
* The chemistry of Double-Bonded practical teams (Volume three, 2 parts)
* The chemistry of Organophosphorus Compounds (Volume 4)
* The chemistry of Halides, Pseudo-Halides and Azides (Volume 2, 2 parts)
* The chemistry of the Amino, Nitro and Nitroso teams (2 volumes, 2 parts)
* The chemistry of Dienes and Polyenes (2 volumes)
* The chemistry of natural Derivatives of Gold and Silver
* The chemistry of natural Silicon Compounds (2 volumes, four parts)
* The chemistry of natural Germanium, Tin and Lead Compounds (Volume 2, 2 parts)
* The chemistry of Phenols (2 parts)
* The chemistry of Organolithium Compounds (2 parts)
* The chemistry of Cyclobutanes (2 parts)
* imminent Titles
* The chemistry of Peroxides (Volume 2, 2 parts)
* The chemistry of Organozinc Compounds
* The chemistry of Anilines

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Extra resources for The Chemistry of Organolithium Compounds.

Example text

Throughout the temperature range 166 K to 246 K the NCH3 resonance is sharp and unchanged. It was proposed that the t-butyl group of 14žPMDTA is unsymmetrically sited with respect to the coordinated PMDTA (Figure 6). The partial averaging of N(CH3 )2 resonances and the averaging of CH2 resonances all at lower temperatures was ascribed to fast rotation of coordinated PMDTA around the C−Li bond. Then, above 206 K, averaging of the broadened N(CH3 )2 doublet would be due to fast local reversible dissociation of N−Li coordination accompanied by inversion at nitrogen and rotation around the C−N bond prior to N−Li recombination.

There are four required elements of the density matrix, α |β , being one of the spin states of 7 Li. Because we use the quadrupole relaxation operator at the extreme narrowing limit, just one composite relaxation parameter jq suffices to account for the contribution of 7 Li quadrupolar relaxation to the 13 C NMR line shape in this system (see equation 63), jq = 2 e2 Q h 1 30 τq (63) where Q, q and τq , are, respectively14, 16 , the 7 Li quadrupole moment, the electric field gradient and the quadrupolar correlation time.

Intermolecular C−Li exchange between dimeric organolithium compounds via a cubic tetramer 1. Dynamics of the reorganization behavior of organolithium compounds 29 TABLE 5. 0 ± 2 C−6 Li bonds in monomer, (21) thus averaging the 13 C−6 Li coupling constants. * Li Ph*Li* + PhLi Ph* Ph PhLi* + Ph*Li (94) Li (21) (22) Note that the averaging of a coupling constant to zero in the absence of relaxation effects is diagnostic for bimolecular exchange kinetics. X-ray crystallography has demonstrated that in the solid state TMEDA is bidentately complexed with Li bridged dimeric phenyllithium26 .

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