79082-91-0Relevant articles and documents
Exploring the Reactivity of Donor-Stabilized Phosphenium Cations: Lewis Acid-Catalyzed Reduction of Chlorophosphanes by Silanes
Pearce, Kyle G.,Borys, Andryj M.,Clark, Ewan R.,Shepherd, Helena J.
supporting information, p. 11530 - 11536 (2018/09/21)
Phosphane-stabilized phosphenium cations react with silanes to effect either reduction to primary or secondary phosphanes, or formation of P-P bonded species depending upon counteranion. This operates for in situ generated phosphenium cations, allowing catalytic reduction of P(III)-Cl bonds in the absence of strong reducing agents. Anion and substituent dependence studies have allowed insight into the competing mechanisms involved.
Phosphenium-insertion and chloronium-addition reactions involving the cyclo-phosphanes (t-BuP)n (n≤3, 4)
Holthausen, Michael H.,Knackstedt, Dane,Burford, Neil,Weigand, Jan J.
, p. 1155 - 1162 (2013/10/22)
The transfer of a Ph2P+-moiety provided by Ph2PCl and chloronium-addition with PCl5 or PhICl2 to the cyclo-phosphanes (t-BuP)n (n≤3 (4), 4 (5)) were investigated. The reactions strongly depend on the presence of GaCl3 or Me3SiOTf as a halide abstracting reagent. The reaction of 4 with Ph2PCl and GaCl3 quantitatively yields cation [Ph2P(t-BuP)3]+ (6+) as a GaCl4 - salt. Using Me3SiOTf as a halide abstracting reagent leads to the ring expansion of (t-BuP)3 (4) to tetrameric (t-BuP)4 (5) and cation 6+ is only formed as a minor product. Chloronium addition employing the PCl5/GaCl3 or PhICl2/Me3SiOTf systems as Cl+-sources to 4 gives complex reaction mixtures. In contrast, the Cl+-addition to 5 gives cation [Cl(t-BuP)4]+ (8+) quantitatively when the system PCl5/GaCl3 is used. Utilising PhICl2 in the presence of Me3SiOTf gives t-BuPCl2 as the main product.
Ditelluride-promoted diphosphene transfer from a cyclotriphosphane to 2,3-dimethylbutadiene: characterization of di(aryltelluro)diphosphanes
Meyer, H. U.,Severengiz, T.,Mont, W. W. du
, p. 691 - 694 (2007/10/02)
The cleavage of tri-tert-butylcyclotriphosphane 1 with di(4-methylphenyl)ditelluride 2 leads to 1,2-di-tert-butyl-1.2-di(4-methylphenyltelluro)diphosphane 3 and tetra-tert-butylcyclotetraphosphane.When 1 is heated with 2 in the presence of 2,3-dimethylbutadiene, the diphosphene trapping product 1,2-di-tert-butyl-4,5-dimethyl-1,2-diphosphacyclohex-4-ene 5 can be detected.The salt elimination reaction of tert-butyldichlorophosphane with 4-methylphenyltellurotelluromagnesium bromide leads mainly to 3 and ditelluride 2.Tellurophosphane 6 and 1,2-di-tert-butyl-1,2-di(aryltelluro)diphosphanes 3. 7 (7 : aryl = 2,4,6-triisopropylphenyl) are available in fair yields from di-tert-butylchlorophosphane or 1,2-di-tert-butyl-1,2-dichlorodiphosphane with metal tellurolates.At 90 deg C with 2,3-dimethylbutadiene, 7 acts as a source of 1,2-di-tert-butyldiphosphene trapped as cycloadduct 5. - Keywords: cyclophosphanes / phosphorus-carbon heterocycles / cleavage of phosphorus-phosphorus bonds / di(aryltelluro) diphosphanes / diphosphene transfer.