Phosphino Carboxylic Acid Ester Functionalized Carbosilane Dendrimers: Nanoscale Ligands for the Pd-Catalyzed Hydrovinylation Reaction in a Membrane Reactor
作者:Eva B. Eggeling、Neldes J. Hovestad、Johann T. B. H. Jastrzebski、Dieter Vogt、Gerard van Koten
DOI:10.1021/jo000433k
日期:2000.12.1
Phosphino carboxylicacidester terminated G(0) compounds Si(CH(2))(3)SiMe(2)(C(6)H(4)CH(2)OC(O)(CH(2))(n)()CH(2)PPh(2)(4) (9a and 9b; n = 1, 2) and the carbosilane dendrimers Si(CH(2))(3)Si((CH(2))(3)SiMe(2)(C(6)H(4)CH(2)OC(O)(CH(2))(n)()CH(2) PPh(2))(3)(4) (10a and 10b; n = 1, 2) have been prepared as hemilabile nanoscale ligands for the palladium-catalyzed codimerization of olefins. The hydrovinylation
膦酸酯封端的G(0)化合物Si(CH(2))(3)SiMe(2)(C(6)H(4)CH(2)OC(O)(CH(2))(n) ()CH(2)PPh(2)(4)(9a和9b; n = 1,2)和碳硅烷树状大分子Si(CH(2))(3)Si((CH(2))(3)SiMe (2)(C(6)H(4)CH(2)OC(O)(CH(2))(n)()CH(2)PPh(2))(3)(4)(10a和10b ; n = 1,2)制备为钯的烯烃共聚二聚体的半不稳定的纳米级配体,苯乙烯的乙烯基化反应在连续操作的纳滤膜反应器中进行,在连续条件下,反应的选择性大大提高。比较了单体模型配合物和树枝状催化剂在间歇反应中的活性和选择性,由树枝状配体和(烯丙基)钯(II)前体原位制备了Pd催化剂配合物。