A rhodium-catalyzed exchange reaction of diphosphine disulfides, a diphosphine oxide, and a diphosphine is developed. Various symmetric diphosphine disulfides containing alkyl and phenyl groups are exchanged, giving equilibrium mixtures, from...
Dialkyl(heteroaryl)phosphine sulfides were synthesized by the rhodium‐catalyzed exchange reaction of heteroaryl aryl sulfides and tetraalkyldiphosphine disulfides. The reaction has a broad applicability, giving diverse dialkyl(heteroaryl)phosphine sulfides containing five‐ and six‐membered heteroaryl groups. Various dialkyl(heteroaryl)phosphines were obtained by desulfurization.
Reaction of Mn2(CO)10 with R2P(S)P(S)R2 (R=Me, Et, Prn, Bun) in toluene at 120 °C yields binuclear [Mn2(CO)8(μ-PR2)2] and trinuclear [Mn(CO)3(μ-SPR2)]3 complexes. Both result from phosphorus–phosphorus bond scission, while in the former sulfur abstraction has also occurred. An X-ray diffraction study of [Mn2(CO)8(μ-PBun2)2] confirms that the manganese adopts a distorted octahedral geometry with local
Oxidation of Diphosphine Dioxides, Disulfides and Phosphinothioite and Photolysis of Diphosphine Disulfides. Formation of Phosphinic and Phosphinothioic Anhydrides
作者:Tateki Emoto、Renji Okazaki、Naoki Inamoto
DOI:10.1246/bcsj.46.898
日期:1973.3
yields of V increased with reaction temperature and with reaction time, indicating a homolytic fission of the P(S)–P(S) bond. Reaction of tetraphenyldiphosphine disulfide with sulfur in refluxing o-dichlorobenzene gave bis(diphenylphosphinothioyl) sulfide. Photolysis of II with a low pressure mercury lamp gave phosphinic acid and sulfur under oxygen, and gave phosphine sulfide and O-methyl phosphinothioate
四苯基二氧化膦与等摩尔量的过苯甲酸 (III) 氧化得到二苯基次膦酸酐,收率良好。类似地,二硫化二膦 (II) 与 III 的 1.5-2.0 摩尔倍,得到相应的硫代膦酸酐 (V),以及相应的次膦酸和硫。II 在回流的二甲苯或邻二氯苯中在空气中得到 V。V 的产率随着反应温度和反应时间的增加而增加,表明 P(S)-P(S) 键的均裂。二硫化四苯基二膦与硫在回流的邻二氯苯中反应得到双(二苯基硫代膦)硫化物。在氧气下用低压汞灯光解 II 得到次膦酸和硫,并在甲醇中得到硫化膦和 O-甲基硫代膦酸酯。