Synthesis of Poly(silyl ether)s by Rhodium(I)-NHC Catalyzed Hydrosilylation: Homogeneous versus Heterogeneous Catalysis
作者:Guillermo Lázaro、Manuel Iglesias、Francisco J. Fernández-Alvarez、Pablo J. Sanz Miguel、Jesús J. Pérez-Torrente、Luis A. Oro
DOI:10.1002/cctc.201200309
日期:2013.5
both the homogeneous and the heterogeneous catalysts, in which the homogeneous system is the more active. Interestingly, the heterogeneous catalyst is reusable. Both homo‐ and heterogeneous catalysts are also effective for the copolymerization of terephthalaldehyde and 1,1,3,3,5,5‐hexamethyltrisiloxane, which affords the corresponding poly(silyl ether). The catalyst yields the heterogeneous system polymers
1-(3-三异丙氧基甲硅烷基丙基)-3-(2-甲氧基乙基)-咪唑鎓溴化物或氯化物盐的制备及其与[Rh(COD)(μ-OMe)] 2(COD = 1,5-环辛二烯)的反应为给出了相应的[Rh(COD)(NHC)X](X = Br,Cl; NHC = 1-(3-三异丙氧基甲硅烷基丙基)-3-(2-甲氧基乙基)-2-丙二烯-咪唑)种类。这些新化合物被用作苯乙酮氢化硅烷化的催化剂前体。铑-氯化物配合物的较高活性表明在催化剂活化中有明显的卤化物作用。将催化前体[Rh(COD)(NHC)Cl]固定在可流动的晶体材料41(MCM-41)上可以制备相应的非均相催化剂。苯乙酮还原为PhMeCH-O-SiMe(OSiMe 3)2通过1,1,1,3,5,5,5,5-七甲基三硅氧烷的氢硅烷化反应可被均相和非均相催化剂有效地催化,其中均相体系更具活性。有趣的是,非均相催化剂是可重复使用的。均相和非均相催化剂对对苯甲醛和1