ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
X-Ray Crystal-Structure Analysis of 2,4,6-Tri(tert-butyl)phenyllithium · N,N,N′,N′-Tetramethylpropane-1,2-diamine: a Monomeric Organolithium CompoundTri(tert-butyl)phenyllithium is an important reagent for the preparation of derivatives of main-group elements with low coordination state as well as a highly hindered base for the generation of amine-free Li-enolates. Its monomeric nature in solution was previously deduced from NMR measurements. While Et2O, THF, and N,N,N′,N′-tetramethylethylene-1,2-diamine (tmen) led to crystalline samples which were not suitable for structure analysis, the N,N,N′,N′-tetramethylpropane-1,2-diamine (tmpn) gave good single crystals of the title compound from Et2O/hexane (disorder along the two-fold crystallographic axis running through Li—C(1) and C(4) of the Ph ring. The structure (Fig. 1, Table 1) has some remarkable features: (i) it is one of the very few monomeric organolithium compounds so far, (η1-Li on aromatic ring); (ii) it has the rare trigonal-planar coordination of the Li-atom; iii) there are close contacts between the Li-atom arid one of the Me groups in each ortho-position (Fig. 3). The internal angle on the Ph-ring ipso-C-atom is 114°. This angle as well as those of the other known phenyllithium (Table 2), -magnesium, and -aluminum structures are included in a plot of ipso-angles against Pauling electronegativities (Fig. 2).
Notes:
No abstract.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19890720321
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