ISSN:
0947-6539
Keywords:
basicity
;
hydrogen bonds
;
organosilicon compounds
;
zwitterions
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The high basicity of {2,6-bis-[(dimethylamino) methyl]phenyl} bis (1,2-benzenediolato)silicate (1) was demonstrated by its quantitative protonation in methanol to give the zwitterion 2. It was found that 1 is much more basic (pKa in CH2Cl2 = 16.7) than the “proton sponge” 1,8-bis(dimethylamino)naphthalene (3) and also much more basic than {2,6-bis-[(dimethylamino) methyl]phenyl} bis (1,2-benzenediolato)phosphorane (4). The stability of the zwitterion 2, the geometry of which corresponds to a more perfect octahedron than 1, can explain the high basicity of 1. Dynamic NMR studies of 2 in solution show that at low temperature the hydrogen-bonding interaction with one oxygen atom observed in the solid state is maintained. On raising the temperature, firstly the hydrogen bond breaks, then dynamic coordination occurs, in which the NMe2 groups displace each other in conjunction with transprotonation.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19960020316
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