ChemInform Abstract: New Selenium ‐ Nitrogen Compounds: tert‐Butyl‐seleninylamine, tBuNSeO, and Di(tert‐butyl)selenium Diimide, Se(NtBu)₂.

Abstract

On reaction oftBuNHz (I) with Se‐ OClz, at molar ratio 3:1, the seleninylamine (II) is obtained as the first representative of this class of compounds.

2. Selenium– and tellurium–halogen reagents

“…have used (C6H5)2SeF2 as the starting material (Section 3.2) [4]. Selenium tetrachloride is, however, a convenient source of selenium(IV) for the preparation of selenium(IV) diimides RN=Se=NR by reaction with the appropriate primary amine RNH2 (R = t Bu [5] Ad [6a]) or the monolithiated primary i Pr, neo-pentyl, CF3CH2) has been prepared by the reaction of the appropriate alcohol with SeCl4 in the presence of trimethylamine; however, the R = Me or Et derivatives are thermally unstable [7]. By contrast, ethylene glycol, pinacol and neopentyl glycol give selenuranes that can be isolated as white crystalline solids [7].…”

Selenium– and tellurium–nitrogen reagents

“…Owing to the insolubility of the reactants in this synthesis, a subsequent modification involved the use of the more soluble 2-nitrobenzenesulfonamide (NsNClNa) for the generation of NsN=Se=NNs [69]. This in situ reagent reacts in a manner similar to selenium dioxide in the allylic amination of olefins and 1,2-diamination of 1,3-dienes (Figure 4.11) [69] The thermally unstable dialkyl selenium(IV) diimides RN=Se=NR (R = t Bu, Ad) (Ad = adamantyl) have been isolated as an oil or yellow crystals, respectively, from the reaction of the appropriate primary alkylamine with SeCl4 [70,71]; the introduction of supermesityl substituents (R = Mes* = 2,4,6-t Bu3C6H2) enhances the thermal stability of the selenium(IV) diimide [72]. The X-ray analyses of RN=Se=NR (R = Ad, Mes*) reveal monomeric structures in the solid state [71,72].…”

Selenium– and tellurium–halogen reagents

“…have used (C6H5)2SeF2 as the starting material (Section 3.2) [4]. Selenium tetrachloride is, however, a convenient source of selenium(IV) for the preparation of selenium(IV) diimides RN=Se=NR by reaction with the appropriate primary amine RNH2 (R = t Bu [5] Ad [6a]) or the monolithiated primary amine Mes*N(H)Li [6b]; the applications of RN=Se=NR reagents are discussed in Chapter 4, Section 7.1. However, the analogous reaction of SeCl4 with MesNHLi does effect reduction to afford the selenium(II) diamide Se[N(H)Mes]2 [6b].…”

“…The reaction of the primary amine t BuNH2 with SeOCl2 in a 3:1 molar ratio in diethyl ether at -10 o C produced the first selenenylamine t BuNSeO as a brown-orange oil (90 % yield) [5], which can be recrystallised from THF at -20 o C to reveal a dimeric structure [6]. In the case of diamines, e.g.…”