Dyer Philip, Baceiredo Antoine, Bertrand Guy
Laboratoire de Chimie de Coordination du CNRS, 205, route de Narbonne, 31077 Toulouse Cédex, France.
Inorg Chem. 1996 Jan 3;35(1):46-50. doi: 10.1021/ic950628o.
Trifluoromethanesulfonic acid reacts at 240 K with bis[bis(diisopropylamino)phosphino]diazomethane, 1, affording the corresponding cationic (phosphino)(P-hydrogenophosphonio)diazomethane derivative 2, which eliminates dinitrogen above 250 K, leading to (phosphino)(phosphonio)carbene 3 isolated in 76% yield (mp 88 degrees C). Bis(diisopropylamino)phosphenium salt 5a adds at 240 K to P-chlorodiazomethylenephosphorane 4 giving (phosphino)(P-chlorophosphonio)diazo derivative 6a, which leads, after N(2) elimination, to the corresponding carbene 7a. Addition of potassium tert-butoxide to 3 gives rise to the transient diphosphinocarbene 8, which rearranges into phosphaalkene 9. Sodium tetrafluoroborate, tert-butyllithium, and tributyltin hydride react with 3 to afford P-fluoro-P'-hydrogenocarbodiphosphorane 10, P,P'-dihydrogenocarbodiphosphorane 12, and stannyl-substituted methylene salt 15, respectively. tert-Butyl isocyanide reacts with phosphoniocarbene 3 giving heterocycle 19, whereas with carbene 7 phosphonioketeneimine 18 and bis(diisopropylamino)phosphinonitrile are obtained.
三氟甲磺酸在240 K下与双[双(二异丙基氨基)膦基]重氮甲烷1反应，生成相应的阳离子(膦基)(P -氢膦鎓)重氮甲烷衍生物2，该衍生物在250 K以上消除氮气，生成产率为76%（熔点88摄氏度）的(膦基)(膦鎓)卡宾3。双(二异丙基氨基)鏻盐5a在240 K下与P -氯重氮亚甲基膦烷4反应，生成(膦基)(P -氯膦鎓)重氮衍生物6a，该衍生物在消除N₂后生成相应的卡宾7a。向3中加入叔丁醇钾会生成瞬态二膦基卡宾8，其重排为磷烯9。四氟硼酸钠、叔丁基锂和三丁基氢化锡分别与3反应，得到P -氟 - P'-氢碳二膦烷10、P,P'-二氢碳二膦烷12和锡基取代的亚甲基盐15。叔丁基异氰酸酯与膦鎓卡宾3反应生成杂环19，而与卡宾7反应则得到膦鎓乙烯酮亚胺18和双(二异丙基氨基)膦腈。
