Regioselective hydrogenation of dienes catalyzed by palladium–aminosilane complexes grafted on MCM-41
Regioselective hydrogenation of dienes catalyzed by palladium–aminosilane complexes grafted on MCM-41
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MCM-41 接枝钯-氨基硅烷配合物催化二烯的区域选择性加氢
DOI：
10.1016/s1381-1169(01)00508-8
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发表时间：
2002
影响因子：
--
通讯作者：
T. Uematsu
中科院分区：
文献类型：
--
作者：
S. Shimazu;N. Baba;N. Ichikuni;T. Uematsu
通过乙酸钯(II)与接枝在MCM-41上的3-(2-氨基乙基)氨基丙基(AEAPSi)基团的络合制备了负载在MCM-41上的钯(II)-氨基硅烷络合物(Pd-AEAPSi/MCM (1))。 FT-IR 和13C CP MAS NMR 研究表明AEAPSi 与钯(II) 螯合形成Pd(II)-AEAPSi 络合物。将得到的1作为催化剂进行二烯的区域选择性氢化。 Pd-AEAPSi/MCM 对于带有羟基的二烯（如香叶醇和芳樟醇）表现出非常高的反应速率，而对于没有 OH 基团的柠檬烯，反应速率明显较低。 MCM负载的催化剂在具有OH基团的二烯氢化中也表现出显着的高区域选择性。这些结果表明 MCM-41 表面和基材之间的亲水相互作用在速率决定步骤中起着重要作用。
A palladium(II)–aminosilane complex supported on MCM-41 (Pd–AEAPSi/MCM (1)) was prepared by the complexation of palladium(II) acetate to 3-(2-aminoethyl)aminopropyl (AEAPSi) groups grafted on MCM-41. FT-IR and13C CP MAS NMR studies indicated that AEAPSi chelated to palladium(II) to form the Pd(II)–AEAPSi complex. Regioselective hydrogenation of dienes was carried out by the obtained 1 as a catalyst. Pd–AEAPSi/MCM exhibited remarkably high reaction rates for the dienes with a hydroxyl group such as geraniol and linalool, while for limonene without OH group the reaction rate was notably low. The MCM-supported catalyst also showed noticeably high regioselectivity in the hydrogenation of dienes with OH group. These results indicate that the hydrophilic interaction between the MCM-41 surface and the substrates plays an important role in the rate-determining step.