ISSN:
0009-2940
Keywords:
Triaminobenzenes / σ-Complexes, stable halogeno / Electron transfer
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Aminobenzenes, 21. - Electron Transfer in the Reactions of Halogeno G-complexes of 1.3.5-Tris(l-pyrrolidinyl)benzene with NucleophilesIodo, bromo, chloro, and thiocyanato σ-complexes 4, accessible as crystalline compounds from 1,3,5-tris(1-pyrrolidinyl)benzene (1) with halogens and dirhodan, respectively, react with nucleophiles or bases under dehalogenation, deprotonation, dimerization, or H σ-complex formation. The product formation depends on the redox potentials of the σ-complexes (acceptors) and the nucleophiles (donors), on the leaving tendency of the substituents on C-1 of the σ-complexes, and on the reaction time. The unexpected reactions are interpreted by an electron transfer from the nucleophile Y| to the σ-complex A+ to give the radical A*, a subsequent heterolytic dissociation to the 1,3,5-tris(1-pyrrolidinyl)benzene radical cation C.+, and its follow-up reactions (addition of nucleophiles, dimerization, and H abstraction). The H σ-complex 6 results the most stable final product after long reaction times because of its lowest acceptor properties and the poor nucleofugal leaving tendency of a hydride ion.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19901230132
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