Synthesis and characterization of cationic selenium-nitrogen heterocycles from tert-butyl-DAB (DAB = 1,4-di-tert-butyl-1,3-diazabutadiene) and SeX 4via the reductive elimination of X2 (X = Cl, Br): A distinct contrast with tellurium

被引：36
作者：
Department of Chemistry, University of Western Ontario, 1151 Richmond St., London, ON N6A 5B7, Canada [1 ]
不详 [2 ]
机构：
[1] Department of Chemistry, University of Western Ontario, London, ON N6A 5B7
[2] Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON N9B 3P4
来源：
Dalton Trans. | 2008年 / 26卷 / 3470-3477期
关键词：
Chelation;
D O I：
10.1039/b719779a
中图分类号：
学科分类号：
摘要：
The synthesis and comprehensive characterisation of a series of 1,2,5-selenadiazolium salts, which were generated from the direct reaction between the neutral bidentate ligand tert-butyl-DAB and a variety of heavy chalcogen halides, are reported. The formation of the cationic heterocycle from the reaction of SeX4 (X = Cl, Br) and the ligand results in a two electron redox process where the chalcogen undergoes a two electron reduction concomitant with the elimination of X2, the oxidation by-product. A reaction pathway for this chemistry has been proposed necessitating several key intermediates. These species have been synthesized and used in a stepwise series of transformations that strongly supports this very unusual reactivity for the chalcogens. In contrast, the reaction between tert-butyl DAB and TeX4 (X = Cl, Br, I), does not result in redox, rather an octahedral Te(iv)•DAB complex is formed or no reaction was observed. © 2008 The Royal Society of Chemistry.
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页码：3470 / 3477
页数：7
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