When the tri-tert-butylcyclopropenylphosphane 5 is allowed to react with ketenes 6, the cyclopropenyl(silyl)vinylphosphanes 7 are obtained. Subsequent acylation proceeds via silyl exchange to furnish the phosphanes 8 while methanolysis gives rise to the secondary phosphanes 9 by way of P/Si bond cleavage. Sodium hydroxide catalyzed elimination of hexamethyldisiloxane from 7 results in the formation of the 1-phosphaallenes 10. The P/C double bonds of the latter can be saturated by either 1,2-addition (→ 11, 12) or by oxidative addition (→ 13) followed by addition of water (→ 14). Complexation of 10 with the metal fragments W(CO)5 or Fe(CO)4 moieties yields the novel metal complexes 15 and 16.
当三叔丁基环
丙烯基膦 5 与
烯酮 6 反应时,就会得到环
丙烯基(
硅烷基)
乙烯基膦 7。随后通过
硅烷交换进行酰化,得到膦 8,而
甲醇分解则通过 P/Si 键裂解得到仲膦 9。在
氢氧化钠催化下,7 中的六
甲基二
硅氧烷被消除,生成 1-膦
烯 10。后者的 P/C 双键可通过 1,2-加成(→11、12)或
氧化加成(→13)后加
水(→14)达到饱和。10 与
金属片段 W(CO)5 或 Fe(CO)4 分子络合,可生成新型
金属配合物 15 和 16。