作者:Ralf A. Findeis、Lutz H. Gade
DOI:10.1039/b209589k
日期:2003.1.8
The synthesis of two novel types of tripodal phosphine ligands containing vinyl and alkynyl linker functions in their ligand backbones are reported. Using pentaerythritol (1) as the starting material the functionalized phosphines H2CCH–CH2OCH2C(CH2PPh2)3
(6), Me3SiCC–CH2OCH2C(CH2PPh2)3
(10) and HCC–CH2OCH2C(CH2PPh2)3
(11) were obtained in good yield in 4–5-step syntheses. H2CCH–CH2OCH2C(CH2PPh2)3
(6) and the silyl protected alkinyl derivative (CH3)3Si–CC–CH2OCH2C(CH2PPh2)3
(10) were reacted with one molar equivalent of [Mo(CO)3(MeCN)3] to yield the yellow-brown, air stable triphosphine–molybdenum complexes [H2CCH–CH2OCH2C(CH2PPh2)3}Mo(CO)3]
(12) and [(CH3)3Si–CC–CH2OCH2C(CH2PPh2)3}Mo(CO)3]
(13) the latter of which was characterized by X-ray diffraction.
报告了一种包含乙烯和炔烃连接基团的两种新型三足膦配体的合成。以五羟甲基戊烷(1)作为起始材料,通过4至5步合成得到了功能化磷配体H2CCH–CH2OCH2C(CH2PPh2)3 (6)、Me3SiCC–CH2OCH2C(CH2PPh2)3 (10)和HCC–CH2OCH2C(CH2PPh2)3 (11),产率良好。H2CCH–CH2OCH2C(CH2PPh2)3 (6)和硅保护的炔烃衍生物(CH3)3Si–CC–CH2OCH2C(CH2PPh2)3 (10)与一个当量的[Mo(CO)3(MeCN)3]反应,生成了黄色棕色、空气稳定的三膦-钼配合物[H2CCH–CH2OCH2C(CH2PPh2)3}Mo(CO)3] (12)和[(CH3)3Si–CC–CH2OCH2C(CH2PPh2)3}Mo(CO)3] (13),后者通过X射线衍射进行了表征。