Highly Fluorous Bidentate Phosphines
Highly Fluorous Bidentate Phosphines
复制标题
高氟双齿膦
DOI：
--
复制
发表时间：
2008
期刊：
影响因子：
--
通讯作者：
George A. Koutsantonis
中科院分区：
文献类型：
--
作者：
B. Berven;George A. Koutsantonis
四氯二膦[Cl_2P（CH_2）_nPCl_2;n = 2-4]与含氟芳香族前体4-溴的反应（全氟己基）苯和4-（全氟己基）苯酚得到一系列氟标记的二膦[（P-C6 F13 C6 H4）2 P（CH 2）nP（C6 H4 C6 F13- P）2 ; n = 2-4]和新的二亚膦酸酯[（P-C6 F13 C6 H4 O）2 P（CH 2）3 P（OC 6 H4 C6 F13- P）2 ]。改进了1，3-双（二氯膦基）丙烷（dcpp）的合成方法，即用三光气对相应的伯膦进行氯化。还合成了含氟二亚胺RN=C（CH 3）C（CH 3）=NR，其中R = P-C6 H4 C6 F13或P-C6 H4 C8 F17，它们是高空气敏感性含磷配体的空气稳定的替代物。所有化合物均用NMR、IR、MS和微量分析等技术进行了表征。用苯基硅烷成功地还原了膦氧化物[（P-C6 F13 C6 H4）2 P（O）（CH 2）nP（O）（C6 H4 C6 F13- P）2 ; n = 2，3]。
The reaction of tetrachlorodiphosphines [Cl 2 P(CH 2 ) n PCl 2 ;n = 2-4] with fluorousaromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenolgave a series of fluorous-tagged diphosphines [( P-C 6 F 13 C 6 H 4 ) 2 P(CH 2 ) n P(C 6 H 4 C 6 F 13 - P) 2 ; n = 2-4] anda new diphosphonite [( P-C 6 F 13 C 6 H 4 O) 2 P(CH 2 ) 3 P(OC 6 H 4 C 6 F 13 - P) 2 ]. The improvedsynthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involvedthe facile chlorination of the corresponding primary phosphine withtriphosgene. Fluorinated diimines RN=C(CH 3 )C(CH 3 )=NR,where R = P-C 6 H 4 C 6 F 13 or P-C 6 H 4 C 8 F 17 havealso been prepared, and were found to be air-stable alternatives tothe highly air-sensitive phosphorus-containing ligands. All compoundswere characterised by a variety of techniques including NMR, IR,MS and microanalysis. The successful reduction of the phosphine-oxides [( P-C 6 F 13 C 6 H 4 ) 2 P(O)(CH 2 ) n P(O)(C 6 H 4 C 6 F 13 - P) 2 ; n = 2,3] withphenylsilane is also presented.