Reaction of Diphosphenes With Elemental Selenium. Isolation and Characterization of Selenadiphosphiranes and Diselenoxophosphorane

Abstract

Sterically protected thermally stable 1,2,3-selenadiphosphirane and diselenoxophosphorane were isolated from the reaction of E-bis-(2,4,6-tri-t-butylphenyl) diphosphene with elemental selenium.

Formation of antimony–sulfur double‐bond compounds and their trapping with nitrile oxides

“…Various double bonds of group 15-group 15 and group 14-group 15 elements have already been reported. As for the lowcoordinated double-bond compounds between group 15 and group 16 elements, dithioxophosphorane [RP(S)‫ס‬S] [2] and diselenoxo-phosphorane [RP(Se)‫ס‬Se] [3], have been synthesized as stable compounds, and thioxophosphines [RP‫ס‬S] [4] and selenoxophosphines [RP‫ס‬Se] [5] stabilized by the coordination of an amino group have been observed in solution by NMR spectroscopy. However, there are no reports about the double bond of antimony with sulfur.…”

Studies on low‐coordinated nitrogen, phosphorus, sulfur, and selenium compounds

“…Reaction of 109 with Se-Et 3 N afforded the selenium analogs of 112 and 114 [114] The phosphine Ar*PH 2 produced the very stable dithioxophosphorane 114 by sulfurization with S 8 and 2,6-lutidine [116]. The synthesis of 114 was reported independently from several laboratories.…”

Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

“…There are a several number of reports on the sulfurization and selenization reactions of diphosphenes [8,16,[18][19][20][21][22] and the related compounds bearing a low-coordinated phosphorus atom, that is, phosphaalkenes [23][24][25][26] and phosphinines [27][28][29]. It was demonstrated that the sulfurization and selenization reactions of diphosphenes should be convenient for obtaining unique heterocyclic compounds such as thia-and selenadiphosphiranes, since the sulfurization reaction of Mes * P PMes * using elemental sulfur in the presence of amine was reported to give the corresponding thiadiphosphirane, Mes * P(S)PMes (2d), as a stable three-membered heterocyclic compound via the corresponding diphosphene monosulfide, Mes * P P( S)Mes * as a metastable intermediate [18,19].…”

“…It was demonstrated that the sulfurization and selenization reactions of diphosphenes should be convenient for obtaining unique heterocyclic compounds such as thia-and selenadiphosphiranes, since the sulfurization reaction of Mes * P PMes * using elemental sulfur in the presence of amine was reported to give the corresponding thiadiphosphirane, Mes * P(S)PMes (2d), as a stable three-membered heterocyclic compound via the corresponding diphosphene monosulfide, Mes * P P( S)Mes * as a metastable intermediate [18,19]. For example, the synthesis of selenadiphosphiranes has been achieved by the treatment of diphosphenes (Mes * P PMes * , Mes * P PMes, Mes = 2,4,6-trimethylphenyl [22], and DisP PDis, Dis bis(trimethylsilyl)methyl [30]) with elemental selenium. We have also reported the syntheses and characterization of BbtP(Y)PBbt (Y = S (2c) and Se (3c)) by the chalcogenation reactions of hindered diphosphene, BbtP PBbt, using elemental sulfur and selenium [8,16].…”