Reaction of the diphosphene ArPPAr (Ar = 2,4,6-Bu^t₃C₆H₂) with sulphur: isolation and X-ray structure of the diphosphene monosulphide

Abstract

The diphosphene ArP=PAr (Ar = 2,4,6-But3C6H2) reacts with elemental sulphur to give the stable monosulphide ArP(S)=PAr (2) whose structure was confirmed by an X-ray analysis; when treated with hexamethylphosphorous triamide, (2) reverts to the starting diphosphene but thermal and photochemical isomerisation of (2) gives the thiadiphosphirane ArP-S-PAr.

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

“…In contrast to the sulfurization reaction of Mes * P PMes * reported by Yoshifuji et al [18,19], the corresponding diphosphene monosulfide derivatives, TbtP P( S)Tbt and TbtP P( S)Fc, were not observed during these reactions as judged by 31 P NMR spectroscopy.…”

“…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.…”

“…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].…”

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

“…Diphosphene 109 gave a sulfide Ar*-P(S)‫ס‬P-Ar* 111 with S 8 , and 111 was quantitatively converted to thiadiphosphirane 112 by heating or irradiation [109]. The isomerization was supported by the results of an MO calculation [110].…”

[2+3]Cycloaddition reaction of a kinetically stabilized distibene with a nitrile oxide leading to the formation of a unique heterocyclic compound

“…Above all, the cycloaddition reactions of such heavier π-bond systems were found to be convenient routes to novel heterocyclic systems. For example, Yoshifuji et al reported that the sulfurization and selenization reactions of Mes*P = PMes* afforded the corresponding chalcogenadiphosphiranes (three-membered ring compounds) as the final products [8][9][10][11][12]. In addition, many examples have been reported for the [2+4]cycloaddition reactions of diphosphenes with dienes giving the corresponding six-membered ring compounds containing a P-P bond [1−4].…”